0000000000043246
AUTHOR
Raikko Kivekäs
Borane reaction chemistry. Alkyne insertion reactions into boron-containing clusters. Products from the thermolysis of [6,9-(2-HC[triple bond]C-C5H4N)2-arachno-B10H12].
The stirring of [ortho-(HC[triple bond]C)-C(5)H(4)N] with [nido-B(10)H(14)] in benzene affords [6,9-{ortho-(HC[triple bond]C)-C(5)H(4)N}(2)-arachno-B(10)H(12)] 1 in 93% yield. In the solid state, 1 has an extended complex three-dimensional structure involving intramolecular dihydrogen bonding, which accounts for its low solubility. Thermolysis of 1 gives the known [1-(ortho-C(5)H(4)N)-1,2-closo-C(2)B(10)H(11)] 2 (13%), together with new [micro-5(N),6(C)-(NC(5)H(4)-ortho-CH(2))-nido-6-CB(9)H(10)] 3 (0.4%), [micro-7(C),8(N)-(NC(5)H(4)-ortho-CH(2))-nido-7-CB(10)H(11)] (0.4%) , 4 binuclear [endo-6'-(closo-1,2-C(2)B(10)H(10))-micro-(1(C),exo-6'(N))-(ortho-C(5)H(4)N)-micro-(exo-8'(C),exo-9'(N))-(…
Synthesis, reactivity and structural studies of selenide bridged carboranyl compounds.
Reaction of the lithium salt Li[1-R-1,2-closo-C(2)B(10)H(10)] with selenium under mild conditions, followed by hydrolysis gave the diselenide compound (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) in contrast to the well-reported mercapto compounds 1-SH-2-R-1,2-closo-C(2)B(10)H(10) obtained using a similar synthetic procedure. Details for the preparation and X-ray structural characterisation of the new compounds (2-Me-1,2-closo-C(2)B(10)H(10))(2)Se, (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) (R = Me, Ph, ) are specified. To further explore the mechanism of the dimerization reaction, the complex [Au(1-Se-2-Me-1,2-closo-C(2)B(10)H(10))(PPh(3))] was synthesized, confirming the existence of the intermedia…
“Water-stable boron-iodinated dicarbollide dianions [7,8-nido-C2H2B9I9]2−and [7,8-nido-C2H2B9I8H]2−”
The reaction of 3,4,5,7,8,9,10,11,12-I(9)-1,2-closo-C(2)B(10)H(3) with KOH/EtOH gave a mixture of the boron periodinated [1,2,3,4,5,6,9,10,11-I(9)-7,8-nido-C(2)B(9)H(2)](2-) and the highly iodinated on boron [1,2,4,5,6,9,10,11-I(8)-7,8-nido-C(2)B(9)H(3)](2-) in approximately 50% each. Moreover, 3,4,5,6,7,8,9,10,11,12-I(10)-1,2-closo-C(2)B(10)H(2) was reacted with KOH/EtOH to purely produce [1,2,3,4,5,6,9,10,11-I(9)-7,8-nido-C(2)B(9)H(2)](2-). It is the first dinegative dicarbollide stable in water or protic solvent reported in literature.
Synthesis of small carboranylsilane dendrons as scaffolds for multiple functionalizations.
Small carbosilane dendrons in which a closo-carborane is located at the focal point have been prepared by a sequence of steps involving hydrosilylation and reduction reactions. These compounds are used as scaffolds for peripheral functionalization with styrene, chlorovinylstyrene, or suitable carboranes, while keeping the C(cluster)-Si (C(c)-Si) bond. Modification of the core by reduction of the carborane with Mg/BrCH2CH2Br was also achieved.
Restricted rotation in unbridged sandwich complexes: rotational behavior of closo-[Co(eta 5-NC4H4)(C2B9H11)] derivatives.
Rotation about the centroid/ metal/centroid axis in ferrocene is facile; the activation energy is 1-5 kcal mol - 1 . The structurally similar sandwich complexes derived from closo-[3-Co(η 5 -NC 4 H 4 )-1,2-C 2 B 9 H 1 1 ] (1) have a different rotational habit. In 1, the cis rotamer in which the pyrrolyl nitrogen atom bisects the carboranyl cluster atoms is 3.5 kcal mol - 1 more stable in energy than the rotamer that is second lowest in energy. This cis rotamer is wide, spanning 216°, and may be split into three rotamers of almost equal energy by substituting the N and the carboranyl carbon atoms adequately. To support this statement, closo-[3-Co(η 5 -NC 4 H 4 )-1,2-(CH 3 ) 2 -1,2-C 2 B 9 H …
Controlled Direct Synthesis of C-Mono- and C-Disubstituted Derivatives of [3,3′-Co(1,2-C2B9H11)2]− with Organosilane Groups: Theoretical Calculations Compared with Experimental Results
Mono- and dilithium salts of [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-), (1(-)), react with different chlorosilanes (Me(2)SiHCl, Me(2)SiCl(2), Me(3)SiCl and MeSiHCl(2)) with an accurate control of the temperature to give a set of novel C(c)-mono- (C(c) = C(cluster)) and C(c)-disubstituted cobaltabis(dicarbollide) derivatives with silyl functions: [1-SiMe(2)H-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (3(-)); [1,1'-mu-SiMe(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (4(-)); [1,1'-mu-SiMeH-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (5(-)); [1-SiMe(3)-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (6(-)) and [1,1'-(SiMe(3))(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (7(-)). In a similar way, the [8,8'-mu-(1''…
Synthesis, reactivity and structural studies of carboranyl thioethers and disulfides.
The equimolar reaction of 1-SH-2-R-1,2-closo-C2B10H10 (R = Me, H, Ph) with KOH in ethanol produces the thiolate species [1-S-2-R-1,2-closo-C2B10H10]−. These react with iodine to give the disulfide bridged dicluster (1-S-2-R-1,2-closo-C2B10H10)2 (R = H, Me, Ph) compounds as analytically pure, white and air-stable solids in high yield. Synthesis of monothioether bridged species is synthetically more difficult. In fact three procedures have been tested to obtain the thioether bridged dicluster compounds (2-R-1,2-closo-C2B10H10)2S (R = Me, H, Ph) but only (2-Me-1,2-closo-C2B10H10)2S was successfully synthesized and characterized. Attempts to produce mixed compounds (1-R-1,2-closo-C2B10H10)S(1-R…
Interplay of hydrogen bonding and π–π interactions in the molecular complex of 2,6-lutidine N-oxide and water
Abstract The crystal and molecular structure of 2,6-lutidine N-oxide monohydrate (1) has been determined by X-ray diffraction analysis. Each water molecule is acting as bridging ligand between the N→O moieties of two 2,6-lutidine N-oxide molecules through moderate strong intermolecular hydrogen bonding (O–H⋯O, O⋯O distances are 2.787(2) and 2.832 (2) A) giving rise to a one-dimensional (1D) polymeric helical chain. A two-dimensional (2D) layered network is then formed by self-assembly of 1D helical chains via strong π–π interactions of the aromatic rings (interplanar distances 3.385 A). The molecular structure of 1 is compared with that for the already reported molecular structures of 2-ace…
[Et4N][7-Me2S-nido-B11H12]
Tetraethylammonium 7-dimethylsulfanyl-nido-dodecahydroundecaborate, [Et(4)N][7-Me(2)S-nido-B(11)H(12)] or C(8)H(20)N(+).C(2)H(18)B(11)S(-), is a product of the deprotonation of [7-Me(2)S-nido-B(11)H(13)] with KHBEt(3) and precipitation with tetraethylammonium chloride. The effect of removing one endo-terminal H atom is to cause a general contraction of the open-face B-B distances.
1,2-Bis(methylsulfanyl)-1,2-dicarba-closo-dodecaborane(12)
3 pages, 1 figure, 2 tables
Synthesis of Boron-Iodinated o-Carborane Derivatives. Water Stability of the Periodinated Monoprotic Salt
Boron periodination of o-carborane has been achieved by taking account of the fact that B atoms in the cluster are of two types, i.e., those adjacent to both C atoms and the remainder. The high number of nonequivalent leaving groups opens the possibility through B-C coupling to materials with novel possibilities and to self-assembling due to the enhanced polarizability of the C-H bond. Periodination has accentuated the acidity of the carborane, and monoprotic salts are stable in water.
Synthesis, Characterisation and Reactivity towards PdII and PtII of ortho-, meta- and para-Xylyl-Based Phosphorus-Containing Macrocycles
The new meta- and para-xylyl-based phosphadithiamacrocycles 6-phenyl-6-phospha-3,9-dithiabicyclo[9,3,1]pentadeca-1(15),12,14-triene (L2) and 6-phenyl-6-phospha-3,9-dithiabicyclo[9,2,2]pentadeca-1(13),12,14-triene (L3) have been synthesised and characterised. The reactivity of these ligands and the previously described ortho-xylyl macrocycle 6-phenyl-6-phospha-3,9-dithiabicyclo[9,4,0]pentadeca-1(11), 12,14-triene (L1) with [PdCl2(cod)] and K2[PtCl4] has been studied. [MCl2(L)] complexes have been obtained and characterised by NMR spectroscopy. X-ray structural analyses have been carried out in the case of [PdCl2L2]·CH3CN (2·CH3CN) and [PdCl2L3] (3). In both compounds the PdII ion adopts a sl…
Modular Construction of Neutral and Anionic Carboranyl-Containing Carbosilane-Based Dendrimers
A modular construction of new carbosilane dendrimers, which contain four and eight peripheral carborane derivatives and propyl linkages between the C cluster and the Si atoms, has been developed using different methodologies. Regiospecific hydrosilylation of 1-C 6 H 5 -2-(CH 2 CH=CH 2 )-1,2-closo-C 2 B 10 H 10 (1) and 1-CH 3 -2-(CH 2 CH=CH 2 )-1,2-closo-C 2 B 10 H 10 (2) offers an efficient route to molecular precursors and building blocks that can provide both divergent and convergent strategies for dendritic growth. First generations of neutral carboranyl-containing dendrimers were constructed by two approaches: (a) a divergent approach via hydrosilylation of 1 and 2 with the first genera…
Formation of New η5-Rhodium(III) Complexes from η5-Rh(I) Rhodacarborane-Containing Charge-Compensated Ligands
A series of new Rh(I) half-sandwich complexes of formula [3,3-(PPh 3 ) 2 -8-L-closo-3,1,2-RhC 2 B 9 H 1 0 )] (L = SMe 2 (2a), SEt 2 (2b), S(CH 2 ) 4 (2c), SEtPh (2d)) and [1-Me-3,3-(PPh 3 ) 2 -8-L-closo-3,1,2-RhC 2 B 9 H 9 )] (L = SMe 2 (2e), SEt 2 (2f)) have been prepared by reaction of the respective monoanionic charge-compensated ligands [10-L-nido-7,8-C 2 B 9 H 1 0 ] - and [7-Me-10-L-7,8-C 2 B 9 H 9 ] - with [RhCl(PPh 3 ) 3 ]. Complex [3,3-(cod)-8-SMe2-closo-3,1,2-RhC 2 B 9 H 1 0 ] (3) has also been prepared by reaction of K[10-SMe 2 -nido-7,8-C 2 B 9 H 1 0 ] with [RhCl(cod)] 2 . Rh(I) complexes 2a-d may be easily oxidized to the corresponding Rh(III) complexes 4a-d under N 2 atmosphere…
Synthesis and coordinating ability of an anionic cobaltabisdicarbollide ligand geometrically analogous to BINAP.
The anionic chelating ligand [1,1'-(PPh 2 ) 2 -3,3'-Co(1,2-C 2 B 9 H 1 0 ) 2 ] - has been synthesized from [3,3'-Co(1,2-C 2 B 4 H 1 1 ) 2 ] - in very good yield in a one-pot process with an easy work-up procedure. The coordinating ability of this ligand has been studied with Group 11 metal ions (Ag, Au) and with transition-metal ions (Pd, Rh). The two dicarbollide halves of the [1,1'-(PPh 2 ) 2 -3,3'-Co(1,2-C 2 B 9 H 1 0 ) 2 ] - ligand can swing about one axis in a manner analogous to the constituent parts of BINAP and ferrocenyl phosphine derivatives. All these ligands function as hinges, with the most important property in relation to the coordination requirements of the metal being the P…
Synthesis, reactivity and complexation studies of N,S exo-heterodisubstituted o-carborane ligands. Carborane as a platform to produce the uncommon bidentate chelating (pyridine)N-C-C-C-S(H) motif
The synthesis of N,S-heterodisubstituted 1-(2'-pyridyl)-2-SR-1,2-closo-C2B10H10 compounds (R = Et, 2; R = (i)Pr, 3) has been accomplished starting from 1-(2'-pyridyl)-l,2-closo-C2B10H11 (1), and their partial deboronation reaction leading to the structurally chiral [7-(2'-pyridyl)-8-SR-7,8-nido-C2B9H10]-derivatives (R = Et, [4]-; R = (i)Pr, [5]-) has been studied. Capillary electrophoresis combined with the chiral selector alpha-cyclodextrin has permitted the separation of the electrophoretically pure racemic [7-(2'-pyridyl)-8-SR-7,8-nido-C2B9H11]- ions into two peaks each one corresponding to the interaction of one enantiomer with the alpha-cyclodextrin. The N,S-heterodisubstituted o-carbo…
A versatile rigid binucleating ligand for Rh2(μ-Cl)2 moieties: its application as a catalyst in hydrogenation and cyclopropanation
A rigid non-deforming "MCl 2 M" binucleating ligand [7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 ] - able to held the two rhodium atoms in a cooperative distance has been synthesized. The original two bridging chlorides are retained in [Rh 2 (C 5 Me 5 ) 2 Cl 2 {7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 }] + . Hydrogenation of 1-hexene is 10 times faster with [Rh 2 (C 5 Me 5 ) 2 Cl 2 {7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 }] + than with [Rh 2 (C 5 Me 5 ) 2 Cl 4 ]. A hydrogenation mechanism has been proposed which assumes that [Rh 2 (C 5 Me 5 ) 2 (Cl)(H){7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 }] + is the first generated species in the process.
Relevance of the Electronegativity of Boron inη5-Coordinating Ligands: Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide[3,3′-Co(1,2-C2B9H11)2]− Clusters
Regioselective monoalkylation and monoarylation in cobaltabisdicarbollide clusters has been achieved starting from Cs[8-I-3,3'-Co(1,2-C 2 B 9 H 1 0 )(1',2'-C 2 B 9 H 1 1 )] by cross-coupling reactions between a B-I fragment andan appropriate Grignard reagent in the presence of a Pd catalyst and CuT. A considerable number of monoalkylated and monoarylated derivatives have been synthesized, which allowed study of the influence of boron in metallocene-type ligands and the effect of alkyl and aryl substituents on boron in boron anionic clusters. Experimental data from UV/ Vis spectroscopy, E 1 / 2 measurements, and X-ray diffraction analysis, and supported by EHMO and ab initio analyses, indica…
Neutral nido-heteroboranes with non ionisable hydrogen as arenes in coordination
Designed ligands have been synthesised to produce the first arene-like metallacarborane. For arene-like coordination the number of electronegative elements on the coordinating site must be kept to a minimum. Choosing ligands with bulky substituents on the heteroatom allows easy rearrangement and arene-like coordination. This is more hampered the higher the number of hetereoatoms to be re-located.
Amino‐Substituted Ferra‐bis(tricarbollides) − Metallatricarbaboranes Designed for Linear Molecular Constructions
Reactions between high purity FeCl2 and the anion [nido-7-(tBuHN)-7,8,9-C3B8H10)]− (1−) have been used for efficient syntheses of the twelve-vertex double-cluster metallatricarbollide complexes of the para,para (p,p) type [closo-9,9′(RHN)2-commo-2,2′-FeII-1,7,9-(C3B8H10)-1′,7′,9′-(C3B8H10)] (2) (2a, R = tBu and 2b, R = H) (yields 42−45% for 2a). Compound 2b, which contains two reactive amino substituents conveniently attached to the tricarbollide subclusters in p-positions with respect to the metal center, was prepared via facile cleavage of the tBu substituent in 2a either by AlCl3 or by thermal means. The structure of 2b constitutes a good setting for the synthesis of building blocks for …
Carboranyl Substituted Siloxanes and Octasilsesquioxanes: Synthesis, Characterization, and Reactivity
Carboranyl-containing disiloxane, cyclic-siloxane and cage-like silsesquioxane have been prepared in high yields. Two routes are compared for their preparation, a classical hydrolytic process based on hydrolysis and condensation of the freshly prepared carboranylalkylchlorosilane and ethoxysilane precursors and a nonhydrolytic route based on the specific reactivity of chorosilane toward DMSO. Based on the typical reactivity of the carboranyl group toward nucleophiles, dianionic disiloxanes and octaanionic silsesquioxanes were obtained without modification of the siloxane bond. Products are fully characterized by FTIR, NMR and MALDI-TOF methods.
Sulfur, tin and gold derivatives of 1-(2'-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C2B10H10 (R = 2'-pyridyl, X = SH, SnMe3 or AuPPh3).
Reaction of the lithium salt of 1-(2'-pyridyl)-ortho-carborane, Li[1-R-1,2-C(2)B(10)H(10)](R = 2'-NC(5)H(4)), with sulfur, followed by hydrolysis, gave the mercapto-o-carborane, 1-R-2-SH-1,2-C(2)B(10)H(10) which forms chiral crystals containing helical chains of molecules linked by intermolecular S-H...N hydrogen bonds. The cage C(1)-C(2) and exo C(2)-S bond lengths (1.730(3) and 1.775(2)[Angstrom], respectively) are indicative of exo S=C pi bonding. The tin derivative 1-R-2-SnMe(3)-1,2-C(2)B(10)H(10), prepared from Li[1-R-1,2-C(2)B(10)H(10)] and Me(3)SnCl, crystallises with no significant intermolecular interactions. The pyridyl group lies in the C(1)-C(2)-Sn plane, oriented to minimise th…
Sequential Nucleophilic−Electrophilic Reactions Selectively Produce Isomerically Pure Nona‐ B ‐Substituted o ‐Carborane Derivatives
Nine equal substituents on the intensively studied o-carborane have been obtained for the first time by a combined nucleophilic-electrophilic reaction sequence. Iodine and methyl groups have been introduced to prove the generality of the method. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Uncommon coordination behaviour of P(S) and P(Se) units when bonded to carboranyl clusters: experimental and computational studies on the oxidation of carboranyl phosphine ligands.
Oxidation of closo-carboranyl diphosphines 1,2-(PR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr) and closo-carboranyl monophosphines 1-PR(2)-2-R'-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr, Cy; R'=Me, Ph) with hydrogen peroxide, sulfur and elemental black selenium evidences the unique capacity of the closo-carborane cluster to produce uncommon or unprecedented P/P(E) (E=S, Se) and P=O/P=S chelating ligands. When H(2)O(2) reacts with 1,2-(PR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr), they are oxidized to 1,2-(OPR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr). However, when S and Se are used, different reactivity is found for 1,2-(PPh(2))(2)-1,2-closo-C(2)B(10)H(10) and 1,2-(PiPr(2))(2)-1,2-closo-C(2)…
A novel two-dimensional honeycomb-like bimetallic iron(iii)–nickel(ii) cyanide-bridged magnetic material [Ni(cyclam)]3[Fe(CN)6]2·nH2O (cyclam = 1,4,8,11-tetraazacyclodecane)
The 2D honeycomb-like layered iron(iii)–nickel(ii) cyanidebridged complex [Ni(cyclam)]3[Fe(CN)6]2·nH2O exhibits ferromagnetic intralayer and antiferromagnetic interlayer interactions; above 3 K the magnetic properties are typical of a metamagnet with Hc = 5000 G, whereas below 3 K a canted structure is formed, leading to a long range ferromagnetic ordering. Lloret Pastor, Francisco, Francisco.Lloret@uv.es
One-dimensional iron(III) and two-dimensional iron(III)nickel(II) cyanide-bridged ferromagnetic arrays from hexacyanoferrate(III) and [Ni(cyclam)]2+ building blocks: Synthesis, crystal structure and magnetic properties
Abstract The X-ray structures and magnetic properties of a iron(III) linear chain and a honeycomb-like layered iron(III)-nickel(II) cyanide-bridged compound are reported. The former contains alternating iron sites and unexpected ferromagnetic behaviour, justified on the basis of the axial distortion from regular octahedral geometry of one of the iron ions. The latter is metamagnetic with ferromagnetic intralayers and antiferromagnetic interlayers interactions with a Neel temperature, TN= 7.7 K. The field-induced transition from an antiferro- to a ferromagnetic state takes place at Hc= 5000 G. The antiferromagnetic ordered phase exhibits spin-canting and long range ferromagnetic ordering at …
From Mono- to Poly-Substituted Frameworks: A Way of Tuning the Acidic Character of C-c-H in o-Carborane Derivatives
[EN] The incorporation of iodine atoms onto the boron vertices of the o-carborane framework causes, according to spectroscopic data, a uniform increase in the acidic character of the C-c-H (C-c= cluster carbon) vertices, whereas the incorporation of methyl groups onto the boron vertices of the o-carborane framework reduces their acidity. Methyl groups when attached to boron are electron-withdrawing in boron clusters, whereas iodine atoms bonded to boron act as electron donors. This has been proven on B-methyl and B-iodinated o-carboranes with NMR spectroscopy measurements and DFT calculations of natural bond orbital (NBO) charges. which show a Cumulative buildup of positive cluster only tot…
New phosphathiamacrocycles containing polypypiridine units
Abstract A new 2,2′-bipyridine-based phosphadithiamacrocycle: 3,3′-5-phenyl-2,8-dithia-5-phospha[9]-2,2′-bipyridinophane (L) has been synthesized by reacting 6,6′-bis(bromomethyl)-2,2′-bipyridine and dilithium 3-phenyl-3-phosphapenta-1,5-dithiolate. The phosphoryl derivative: 3,3′-5-oxo-5-phenyl-2,8-dithia-5-phospha[9]-2,2′-bipyridinophane (Lox) synthesized by direct oxidation of L at open atmosphere. Both compounds have been isolated as white solids containing different amounts of LiBr. The reaction of acetonitrile solutions of these solids with Fe(II) perchlorate gave the complexes [FeBr(L)](ClO4) · 2H2O and [FeBr(Lox)](ClO4) · 3H2O, which were crystallized as [FeBr(L)]Br · H2O and [ FeBr…
Iodinatedortho-Carboranes as Versatile Building Blocks to Design Intermolecular Interactions in Crystal Lattices
[EN] The crystal structures of numerous iodinated ortho-carboranes have been studied, which has revealed the diversity of intermolecular interactions that these substances can adopt in the solid state. The nature-mostly as it relates to hydrogen and/or halogen bonds-and relative strength of such interactions can be adjusted by selectively introducing substituents onto the cluster, thus enabling the rational design of crystal lattices. In this work we present the newly determined crystal structures of the following iodinated ortho-carboranes: 9-I-1,2-closo-C2B10H11, 4,5,7,8,9,10,11,12-I-8-1,2-closo-C2B10H4, 3,4,5,6,7,8,9,10,11,12-I-10,-1,2-closo-C2B10H2, 1-Me-8,9,10,12-I-4-1,2-closo-C2B10H7,…
Approaches to the preparation of carborane-containing carbosilane compounds.
[Structure: see text] A novel type of carborane cluster assembly has been successfully prepared using carbosilane derivatives as a scaffold. Two synthetic routes have been used: One involves the reaction of a carbosilane containing terminal Si-Cl functions with the lithium salt of the phenyl-o-carborane, and the second one consists of a highly efficient hydrosilylation of tetravinylsilane with the corresponding carboranylsilane. The crystal structure of this carborane-containing carbosilane compound has been determined by X-ray diffraction.
2-Methyl-1-phenylsulfanyl-1,2-dicarba-closo-dodecaborane(12)
In the title o-carborane derivative, C(9)H(18)B(10)S, the methyl and phenylsulfanyl groups are connected to the C atoms of the carborane cage. The C(cage)-C(cage) distance is 1.708 (4) A.
Diferratricarbaboranes of thesubcloso-[(η5-C5H5)2Fe2C3B8H11] Type, the First Representatives of the 13-Vertex Dimetallatricarbaborane Series
Treatment of the [2-Cp-9-tBuNH-closo-2,1,7,9-FeC 3 B 8 H 1 0 ] (1) ferratricarbollide (Cp = η 5 -C 5 H 5 -) with Na + C 1 0 H 8 - in 1,2-dimethoxyethane (DME) at room temperature produced an air-sensitive transient anion with a tentatively identified nido-[tBUNH-CpFeC 3 B 8 H 1 0 ] 2 - constitution. In-situ reaction of this low-stability ion with [CpFe(CO) 2 I] or [CpFe(CO) 2 ] 2 generated three violet diferratricarbaboranes identified as paramagnetic subcloso complexes [4,5-Cp 2 - -4,5,1,6,7-Fe 2 C 3 B 8 H 1 1 ] (2; yield 2%), [4,5-Cp 2 - -4,5,1,7,12-Fe 2 C 3 B 8 H 1 1 ] (3; yield 2%), and [7-tBuNH-4,5-Cp 2 - -4,5,1,7,12-Fe 2 C 3 B 8 H 1 0 ] (4; yield 14%). These first representatives of t…
Influence of the solvent and R groups on the structure of (carboranyl)R2PI2 compounds in solution. Crystal structure of the first iodophosphonium salt incorporating the anion [7,8-nido-C2B9H10]−
The influence of the electron-donor or electron-acceptor capacity of the R groups (R = (i)Pr, Ph, Et) and the solvent on the molecular geometry in solution of adducts of carboranylphosphanes [(carboranyl)(i)Pr2P, (carboranyl)Ph2P and (carboranyl)Et2P] with I2 in 1 : 1 ratios, has been studied in detail by 31P{1H} and 11B{1H} NMR spectroscopies. The more electron-accepting Ph groups make the (carboranyl)Ph2P less nucleophilic, thus stabilizing the I2 encapsulated neutral biscarboranylphosphane-diiodine adducts in solution, such as (carboranyl)Ph2PI-IPPh2(carboranyl), generating P---I-I---P motifs. Even in a polar solvent, such as EtOH, the arrangement is preserved. The expected basicity of t…
Aurophilicity as a cofactor in crystal engineering. Dicyanoaurate(I) anion as a building block in a novel Co(II)–Au(I) bimetallic assembly
A 2D grid-shaped cyanide-bridged Co(II)–Au(I) bimetallic coordination polymer, [Co(DMF)2{Au(CN)2}2], has been prepared from the [Au(CN)2]2 building block; sheets associate pair-wise by aurophilic interactions and the compound exhibits zeolite-like properties. Lloret Pastor, Francisco, Francisco.Lloret@uv.es
Synthesis of quadruped-shaped polyfunctionalized o-carborane synthons
[EN] o-Carborane derivatives with precisely defined patterns of substitution have been prepared from 8,9,10,12-I-4-1,2-closo-C2B10H8 by replacing the iodine atoms, bonded to four adjacent boron vertices in the cluster, with allyl, and subsequently 3-hydroxypropyl groups. The resulting structures, comprising four pendant arms and two reactive vertices located on opposite sides of a central o-carborane core, can be envisaged as versatile precursors for dendritic growth
Two polymorphs Ni(II) complexes containing the dicyanamide ligand: syntheses, structures and magnetic properties of {[Ni(meso-CTH)(μ1,5-dca)]ClO4}n and [Ni(meso-CTH)][Ni(meso-CTH)(dca)2](ClO4)2 (dca=dicyanamide; CTH=meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraaza cyclotetradecane)
Abstract Two polymorphs Ni(II) complexes {[Ni(meso-CTH)(μ1,5-dca)]ClO4}n (1) and [Ni(meso-CTH)][Ni(meso-CTH)(dca)2](ClO4)2 (2) have been obtained in the same synthesis from dicyanamide (dca) and [Ni(meso-CTH)](ClO4)2 and have been characterized by X-ray crystallography and magnetic measurements. Complex 1 is a 1D cationic polymeric zig-zag chain with single end-to-end dca bridges connecting Ni(II) ions in trans positions, whereas in compound 2 coexist two different types of Ni(II) mononuclear units, cationic square-planar and neutral octahedral. Variable-temperature magnetic measurements reveal weak ferromagnetic interactions across the single end-to-end dca bridges in 1, while for 2 the ma…
Formation of Bridging Alkene and Conjugated Dialkenes Exclusively Generated from Alkynes on the [3,3‘-Co(1,2-C2B9H11)2]- Platform. The Unique Hydroboration Role of [3,3‘-Co(1,2-C2B9H11)2]-
The unprecedented metal-mediated transformation of an alkyne into a B,B' bridging alkene is reported. Also, the unprecedented synthesis of a conjugated dialkene derivative of [3,3'-Co(1,2-C2B9H11)2]- generated only from an alkyne, contrary to the usual case where an alkyne and an alkene are needed, is described. This has been possible through the singular capacity of a B-H to produce hydroboration.
A Rational Design for Imidazolate-Bridged Linear Trinuclear Compounds from Mononuclear Copper(II) Complexes with 2-[((Imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL): Syntheses, Structures, and Magnetic Properties of [Cu(L)(hfac)M(hfac)2Cu(hfac)(L)] (M = ZnII, CuII, MnII)
Two mononuclear copper(II) complexes with the unsymmetrical tridentate ligand 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL), [Cu(HL)(H2O)](ClO4)2.2H2O (1) and [Cu(HL)Cl2] (2), have been prepared and characterized. The X-ray analysis of 2 revealed that the copper(II) ion assumes a pentacoordinated square pyramidal geometry with an N3Cl2 donor set. When 1 and 2 are treated with an equimolecular amount of potassium hydroxide, the deprotonation of the imidazole moiety promotes a self-assembled process, by coordination of the imidazolate nitrogen atom to a Cu(II) center of an adjacent unit, leading to the polynuclear complexes [[Cu(L)(H2O)](ClO4)]n (3) and [[Cu(L)Cl].2H2O]n (4). Variab…
Synthesis and solid state structure for a series of poly(1-pyrrolylmethyl)benzene derivatives. Control of the interplaying π–π and C–H⋯π interactions?
The syntheses of new hexa- and 1,2,4,5-tetra-1-pyrrolylmethyl-benzene (1 and 2, respectively) compounds and their crystal structures, along with those for the related disubstituted o-, m- and p-di-1-pyrrolylmethyl-benzene (3–5) derivatives are reported. The arrangements of molecules in the 1-D structure for 2–5 are controlled by the interplay of two different weak interactions: π–π and C–H⋯π (Ph) interactions. The absence of such interactions in the packing of 1 seems to be related to the arrangement of the pyrrolylmethyl arms with respect to the benzene core, which prevents the π cloud of the aromatic ring to be part of any intermolecular interaction. In addition, C–H⋯π (pyrrolyl) interact…
The separation of cis- and trans-1,3-cyclohexanediol isomers by copper complexation. Crystal structures of cis-1,3-cyclohexanediol and copper(II) chloride cis-1,3-cyclohexanediol complex
Abstract A 1:1 complex between copper(II) chloride and cis-1,3-cyclohexanediol has been synthesized and its crystal structure determined. The structure is composed of two different dinuclear [CuCl2(c-13chd)]2 units in which the copper(II) ions are surrounded by the two oxygen atoms of the diol and the two halide ions in a distorted cis-square planar arrangement in both cases. A fifth coordination site is occupied by a halide ion in one dinuclear unit for both copper ions and an O atom belonging to the adjacent CuCl2(c-13chd) moiety in the other dinuclear unit for both copper ions, thus forming a distorted square pyramidal geometry for the metals in all cases. The ability of CuCl2 to prefere…
Novel Bimetallic-Dicyanamide Extended Two- and Three-Dimensional Networks through [Cu(rac-CTH)]2+ Cation Templation
Reaction of [Cu(rac-CTH)]2+ with dicyanamide and Mn2+ or Fe2+ produces three bimetallic extended structures. Complexes 1 and 2, both obtained in the same reaction pot, consist of two different (4,4) two-dimensional (2D) layers, with the [Cu(rac-CTH)(dca)]+ cations noncoordinated and coordinated to the Mn(μ1,5-dca) network for 1 and 2, respectively (rac-CTH = racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Complex 2 shows an unusual monodentate coordination mode through the central amide nitrogen of the dca ligand which is first reported for a polynuclear complex. The structure of 3 consists of a three-dimensional network which can be described as a stacking of layers m…
Highly Stable Neutral and Positively Charged Dicarbollide Sandwich Complexes
Novel sandwich metallacarboranes commo-[3,3'-Ni(8-SMe2-1,2-C2B9H10)2] (1), commo-[3,3'-Co(8-SMe2-1,2-C2B9H10)2]+ (2+), commo-[3,3'-Ru(8-SMe2-1,2-C2B9H10)2] (4) and commo-[3,3'-Fe(8-SMe2-1,2-C2B9H10)2] (5) have been prepared by reaction of [10-SMe2-7,8-nido-C2B9H10]- with NiCl2 x 6 H2O, CoCl2, [RuCl2(dmso)4] and [FeCl2(dppe)], respectively. Reduction of 2+ with metallic Zn leads to the neutral and isolable complex commo-[3,3'-Co(8-SMe2-1,2-C2B9H10)2] (3). Theoretical calculations using the ZINDO/1 semiempirical method show three energy minima for complexes 1-3 and 5 that agree with the presence of three different rotamers in solution at low temperature, while four relative energy minima have…
The [3,3′-Co(1,2-C2B9H11)2]– anion as a platform for new materials: synthesis of its functionalized monosubstituted derivatives incorporating synthons for conducting organic polymers
[3,3′-Co(8-C5H10O-1,2-C2B9H10)(1′,2′-C2B9H11)] (2) was synthesized by reaction of the caesium salt of [Co(C2B9H11)2]− with dimethyl sulfate in the presence of sulfuric acid as catalyst and tetrahydropyrane as solvent; the zwitterionic compound (2) yielded [3,3′-Co(8-C4H4N-(CH2)5-O-1,2-C2B9H10)(1′,2′-C2B9H11)]− (6), [3,3′-Co(8-C8H6N-(CH2)5-O-1,2-C2B9H10)(1′,2′-C2B9H11)]− (7), and [3,3′-Co(8-C12H8N-(CH2)5-O-1,2-C2B9H10)(1′,2′-C2B9H11)]− (8) through the nucleophilic addition of potassium pyrrolyl, indolyl and carbazolyl, respectively. The nucleophilic addition of the same salts on [3,3′-Co(8-C4H8O2-1,2-C2B9H10)(1′,2′-C2B9H11)] (1) yielded, respectively, [3,3′-Co(8-C4H4N-(CH2)2-O-(CH2)2-O-1,2-C…
Recent studies on RR′S·C2B9H11 charge-compensated ligands
Abstract In this paper we report the synthesis of three new carborane derivatives of the series 7,8-R,R′-10-L-7,8-C2B9H9 (R=R′=H, L=SEtPh; R=CH3, R′=H, L=SMe2 and L=SEt2) along with the enhanced characterization of formerly described compounds 7,8-R,R′-10-L-7,8-C2B9H9 (R=R′=H, L=SMe2 (1), L=SEt2 (2) and L=S(CH2)4 (3)). They have been fully characterised using 1H-, 11B- and 13C-NMR spectroscopy. Their bridging proton resonances have been located for the first time. Individual sulfonium substituent contributions have been calculated that have permitted to establish a rule to predict its position in the 1H-NMR spectrum. The crystal structures of 1 and 3 have been resolved for the first time. T…
Designed Synthesis of New ortho-Carborane Derivatives: from Mono- to Polysubstituted Frameworks
The use of nucleophilic and electrophilic processes allow the designed synthesis of several B-iodinated derivatives of o-carborane. Because of the straightforward Pd-catalyzed conversion of B-I to B-C bond with Grignard reagents, such as methylMgBr and biPhenylMgBr, both, symmetrical 3,6-R 2-1,2- closo-C 2B 10H 10 and asymmetrical 3-I-6-Me-1,2- closo-C 2B 10H 10 could be obtained. Not only conventional reactions in solution have been studied but also a highly efficient, clean and fast solvent-free procedure has provided successful results to regioselectively produce B-iodinated o-carborane derivatives by a careful control of the reaction conditions. The high number of nonequivalent leaving …
Methylation and Demethylation in Cobaltabis(dicarbollide) Derivatives
B(8)−R and B(8‘)−R (R = alkyl) disubstituted derivatives of the cobaltabis(dicarbollide) anion [3,3‘-Co(C2B9H11)2]- are reported. The synthesis was achieved by application of a modified Kumada reac...
A solvent-free regioselective iodination route of ortho-carboranes.
Tetraiodo-ortho-carborane based X-ray contrast agents can be readily prepared in a high yield, fast, clean, regioselective fashion by a solvent-free reaction of ortho-carboranes with iodine in sealed tubes.
A Discrete P⋅⋅⋅II⋅⋅⋅P Assembly: The Large Influence of Weak Interactions on the31P NMR Spectra of Phosphane–Diiodine Complexes
Thioethers, except derivatives of [7-R-7,8-C2B9H11] , are more weakly coordinating ligands than phosphanes. This difference is evidenced by the I I distances in the spokeshaped charge-transfer (CT) complexes R2S·I2 and R3P·I2 (Figure 1). The I I distance is sensitive to the strength of the interaction between the s* LUMO orbital on I2 and the HOMO orbital of the donor atom: the stronger the donor, the longer the I I distance. In these spoke CT complexes, the I I distance varies from 3.2 0.2 7 in R3P·I2 adducts [5] to 2.80 0.05 7 in R2S·I2 adducts, [6] indicating the weaker donor character of the thioether group. Whereas extended I2 arrays, spoke adducts of I2, polyiodides, and other structu…
Architecture dependence on the steric constrains of the ligand in cyano-bridged copper(I) and copper(II)-copper(I) mixed-valence polymer compounds containing diamines: crystal structures and spectroscopic and magnetic properties.
A family of cyano-bridged copper(II)-copper(I) mixed-valence polymers containing diamine ligands of formula [Cu(pn)(2)][Cu(2)(CN)(4)] (1, pn = 1,2-propanediamine), [Cu(2)(CN)(3)(dmen)] (2, dmen = N,N-dimethylethylenediamine), and [Cu(3)(CN)(4)(tmen)] (3, tmen = N,N,N',N'-tetramethylethylenediamine) have been prepared with the aim of analyzing how their architecture may be affected by steric constraints imposed by the diamine ligands. In the absence of diamine and with use of the voluminous NEt(4)(+) cation, the copper(I) polymer [NEt(4)][Cu(2)(CN)(3)] (4) forms. The structure of 1 consists of a three-dimensional diamond-related anionic framework host, [Cu(2)(CN)(4)](2-), and enclathrated [C…
Relaxed but highly compact diansa metallacyclophanes.
A series of monoansa [μ-1,1′-PR-3,3′-Co(1,2-C2B9H10)2]− and diansa [8,8′-μ-(1″,2″-benzene)-μ-1,1′-PR-3,3′-Co(1,2-C2B9H9)2]− (R = Ph, tBu) cobaltabisdicarbollidephanes have been synthesized, characterized and studied by NMR, MALDI-TOF-MS, UV-visible spectroscopy, cyclic voltammetry, and DFT calculations. Single crystal X-ray diffraction revealed a highly relaxed structure characterized by the title angle α of 3.8° ([7]−), this being the smallest angle α for a metallacyclophane. In such compounds, the metal-to-phosphorus distance is less than the sum of their van der Waals radii. The availability of a phosphorus lone pair causes an electron delocalization through the metal, as shown by the ab…
CCDC 1425778: Experimental Crystal Structure Determination
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