0000000000156896
AUTHOR
Alexander S. Novikov
PdII-mediated integration of isocyanides and azide ions might proceed via formal 1,3-dipolar cycloaddition between RNC ligands and uncomplexed azide
Reaction between equimolar amounts of trans-[PdCl(PPh3)2(CNR)][BF4] (R = t-Bu 1, Xyl 2) and diisopropylammonium azide 3 gives the tetrazolate trans-[PdCl(PPh3)2(N4t-Bu)] (67%, 4) or trans-[PdCl(PPh3)2(N4Xyl)] (72%, 5) complexes. 4 and 5 were characterized by elemental analyses (C, H, N), HRESI+-MS, 1H and 13C{1H} NMR spectroscopies. In addition, the structure of 4 was elucidated by a single-crystal X-ray diffraction. DFT calculations showed that the mechanism for the formal cycloaddition (CA) of N3− to trans-[PdCl(PH3)2(CNMe)]+ is stepwise. The process is both kinetically and thermodynamically favorable and occurs via the formation of an acyclic NNNCN-intermediate. The second step of the fo…
Metallophilic interactions in polymeric group 11 thiols
Three polymeric group 11 transition metal polymers featuring metallophilic interactions were obtained directly via self-assembly of metal ions and 4-pyridinethiol ligands. In the cationic [Cu2(S-pyH)4]n2+ with [ZnCl4]n2− counterion (1) and in the neutral [Ag(S-py) (S-pyH)]n (2) 4-pyridinethiol (S-pyH) and its deprotonated form (S-py) are coordinated through the sulfur atom. Both ligands are acting as bridging ligands linking the metal centers together. In the solid state, the gold(I) polymer [Au(S-pyH)2]Cl (3) consists of the repeating cationic [Au(S-pyH)2]+ units held together by aurophilic interactions. Compound 1 is a zig-zag chain, whereas the metal chains in the structures of 2 and 3 a…
The H2C(X)–X•••X– (X = Cl, Br) Halogen Bonding of Dihalomethanes
The dihalomethane–halide H2C(X)–X···X– (X = Cl, Br) halogen bonding was detected in a series of the cis-[PdX(CNCy){C(NHCy)═NHC6H2Me2NH2}]X•CH2X2 (X = Cl, Br) associates by single-crystal XRD followed by DFT calculations. Although ESP calculations demonstrated that the σ-hole of dichloromethane is the smallest among all halomethane solvents (the maximum electrostatic potential is only 2.6 kcal/mol), the theoretical DFT calculations followed by Bader’s QTAIM analysis (M06/DZP-DKH level of theory) confirmed the H2C(X)–X···X– halogen bond in both the solid-state and gas-phase optimized geometries. The estimated bonding energy in H2C(X)–X···X– is in the 1.9–2.8 kcal/mol range. peerReviewed
Intermolecular hydrogen bonding H···Cl− in the solid palladium(II)-diaminocarbene complexes
Abstract Weak intermolecular non-covalent H···Cl− interactions in the solid chelated palladium(II)-diaminocarbene complex cis-[PdCl(CNXyl){C(NHXyl)=NHC6H2Me2 NH2}]Cl (3; Xyl=2,6-Me2C6H3) were studied by XRD followed by appropriate DFT calculations. The N–H···Cl contacts for both NH groups in the carbene moiety are different (N1–H···Cl2 3.5258(19), N2–H···Cl2 3.0797(17) Å). The DFT calculations and topological analysis of the electron density distribution within the formalism of Bader’s theory (QTAIM method) were performed for a model cluster of the carbene complex 3. The theoretical data confirmed that the strength of intermolecular HB H···Cl− is different for two NH-protons of the carbene …
Fine-tuning halogen bonding properties of diiodine through halogen–halogen charge transfer – extended [Ru(2,2′-bipyridine)(CO)2X2]·I2 systems (X = Cl, Br, I)
The current paper introduces the use of carbonyl containing ruthenium complexes, [Ru(bpy)(CO)2X2] (X = Cl, Br, I), as halogen bond acceptors for a I2 halogen bond donor. In all structures, the metal coordinated halogenido ligand acts as the actual halogen bond acceptor. Diiodine, I2, molecules are connected to the metal complexes through both ends of the molecule forming bridges between the complexes. Due to the charge transfer from Ru–X to I2, formation of the first Ru–X⋯I2 contact tends to generate a negative charge on I2 and redistribute the electron density anisotropically. If the initial Ru–X⋯IA–IB interaction causes a notable change in the electron density of I2, the increased negativ…
Diversity of Isomerization Patterns and Protolytic Forms in Aminocarbene PdII and PtII Complexes Formed upon Addition of N,N′-Diphenylguanidine to Metal-Activated Isocyanides
Reaction of the palladium(II) and platinum(II) isocyanide complexes cis-[MCl2(CNR)2] [M = Pd, R = C6H3(2,6-Me2) (Xyl), 2-Cl-6-MeC6H3, cyclohexyl (Cy), t-Bu, C(Me)2CH2(Me)3 (1,1,3,3-tetramethylbuth-1-yl abbreviated as tmbu); M = Pt, R = Xyl, 2-Cl-6-MeC6H3, Cy, t-Bu, and tmbu] with N,N′-diphenylguanidine (DPG) leads to DPG-derived metal-bound deprotonated acyclic diaminocarbene (ADC) species. This reaction occurs via a two-step process, involving the initial coupling of the guanidine with one of the isocyanides and leading to deprotonated monocarbene monochelated species, while the next addition grants the deprotonated bis-carbene bis-chelated metal compounds. DPG behaves as nucleophile, depr…
A family of heterotetrameric clusters of chloride species and halomethanes held by two halogen and two hydrogen bonds
Two previously reported 1,3,5,7,9-pentaazanona-1,3,6,8-tetraenate (PANT) chloride platinum(II) complexes [PtCl{HNC(R)NCN[C(Ph)C(Ph)]CNC(R)NH}] (R = tBu 1, Ph 2) form solvates with halomethanes 1·1¼CH2Cl2, 1·1⅖CH2Br2, and 2·CHCl3. All these species feature novel complex-solvent heterotetrameric clusters, where the structural units are linked simultaneously by two C–X⋯Cl–Pt (X = Cl, Br) halogen and two C–H⋯Cl–Pt hydrogen bonds. The geometric parameters of these weak interactions were determined using single-crystal XRD, and the natures of the XBs and HBs in the clusters were studied for the isolated model systems (1)2·(CH2Cl2)2, (1)2·(CH2Br2)2, and (2)2·(CHCl3)2 using DFT calculations and Bad…
Attractive halogen···halogen interactions in crystal structure of trans-dibromogold(III) complex
Abstract A synthesis of the trans-dibromogold(III) t-Bu-Xantphos complex and its self-assembly into infinite 1-dimensional chain in the solid state is reported. The new complex characterized using elemental analyses (C, H, N), ESI-MS, 1H and 13C NMR techniques and X-ray diffraction analysis. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of QTAIM method at the ωB97XD/DZP-DKH level of theory reveal that strength of attractive intermolecular non-covalent interactions Br···Br in the crystal is 1.2–1.6 kcal/mol.
Identification and H(D)-bond energies of C-H(D)Cl interactions in chloride-haloalkane clusters: a combined X-ray crystallographic, spectroscopic, and theoretical study.
The cationic (1,3,5-triazapentadiene)Pt(II) complex [Pt{NH[double bond, length as m-dash]C(N(CH2)5)N(Ph)C(NH2)[double bond, length as m-dash]NPh}2]Cl2 ([]Cl2) was crystallized from four haloalkane solvents giving [][Cl2(CDCl3)4], [][Cl2(CHBr3)4], [][Cl2(CH2Cl2)2], and [][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [][Cl2(CDCl3)4] and [][Cl2(CHBr3)4], the Cl(-) ion interacts with two haloform molecules via C-DCl(-) and C-HCl(-) contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2](-) and [Cl(CHBr3)2](-). In the structures of [][Cl2(CH2Cl2)2] and [][Cl2(C2H4Cl2)2], cations [](2+) are linked to a 3D-network by a syste…
The H2C(X)–X•••X– (X = Cl, Br) Halogen Bonding of Dihalomethanes
The dihalomethane–halide H2C(X)–X···X– (X = Cl, Br) halogen bonding was detected in a series of the cis-[PdX(CNCy){C(NHCy)═NHC6H2Me2NH2}]X•CH2X2 (X = Cl, Br) associates by single-crystal XRD followed by DFT calculations. Although ESP calculations demonstrated that the σ-hole of dichloromethane is the smallest among all halomethane solvents (the maximum electrostatic potential is only 2.6 kcal/mol), the theoretical DFT calculations followed by Bader’s QTAIM analysis (M06/DZP-DKH level of theory) confirmed the H2C(X)–X···X– halogen bond in both the solid-state and gas-phase optimized geometries. The estimated bonding energy in H2C(X)–X···X– is in the 1.9–2.8 kcal/mol range.
Intermolecular hydrogen bonding H···Cl in crystal structure of palladium(II)-bis(diaminocarbene) complex
Abstract The reaction of bis(isocyanide)palladium complex cis-[PdCl2(CNXyl)2] (Xyl=2,6-Me2C6H3) with excess of 4,5-dichlorobenzene-1,2-amine in a C2H4Cl2/MeOH mixture affords monocationic bis(diaminocarbene) complex cis-[PdClC{(NHXyl)=NHC6H2Cl2 NH2}{C(NHXyl)=NHC6H2Cl2NH2}]Cl (3) in moderate yield (42%). Complex 3 exists in the solid phase in the H-bonded dimeric associate of two single charged organometallic cations and two chloride anions according to X-ray diffraction data. The Hirshfeld surface analysis for the X-ray structure of 3 reveals that the crystal packing is determined primarily by intermolecular contacts H–Cl, H–H, and H–C. The intermolecular hydrogen bonds N–H···Cl and C–H···C…
CCDC 1406016: Experimental Crystal Structure Determination
Related Article: Kalle Kolari, Joona Sahamies, Elina Kalenius, Alexander S. Novikov, Vadim Yu Kukushkin, Matti Haukka|2016|Solid State Sciences|60|92|doi:10.1016/j.solidstatesciences.2016.08.005
CCDC 1009210: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1825193: Experimental Crystal Structure Determination
Related Article: Mikhail A. Kinzhalov, Sergey V. Baykov, Alexander S. Novikov, Matti Haukka, Vadim P. Boyarskiy|2019|Z.Krist.Cryst.Mater.|234|155|doi:10.1515/zkri-2018-2100
CCDC 1513981: Experimental Crystal Structure Determination
Related Article: Mikhail A. Kinzhalov, Alexander S. Novikov, Alexander N. Chernyshev and Vitalii V. Suslonov|2017|Z.Kristallogr.|232|299|doi:10.1515/zkri-2016-2018
CCDC 1541823: Experimental Crystal Structure Determination
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1009213: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1009209: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1009215: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1401548: Experimental Crystal Structure Determination
Related Article: Tatiyana V. Serebryanskaya, Alexander S. Novikov, Pavel V. Gushchin, Matti Haukka, Ruslan E. Asfin, Peter M. Tolstoy, Vadim Yu. Kukushkin|2016|Phys.Chem.Chem.Phys.(PCCP)|18|14104|doi:10.1039/C6CP00861E
CCDC 1401547: Experimental Crystal Structure Determination
Related Article: Tatiyana V. Serebryanskaya, Alexander S. Novikov, Pavel V. Gushchin, Matti Haukka, Ruslan E. Asfin, Peter M. Tolstoy, Vadim Yu. Kukushkin|2016|Phys.Chem.Chem.Phys.(PCCP)|18|14104|doi:10.1039/C6CP00861E
CCDC 1542914: Experimental Crystal Structure Determination
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1406018: Experimental Crystal Structure Determination
Related Article: Kalle Kolari, Joona Sahamies, Elina Kalenius, Alexander S. Novikov, Vadim Yu Kukushkin, Matti Haukka|2016|Solid State Sciences|60|92|doi:10.1016/j.solidstatesciences.2016.08.005
CCDC 1009214: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1401550: Experimental Crystal Structure Determination
Related Article: Tatiyana V. Serebryanskaya, Alexander S. Novikov, Pavel V. Gushchin, Matti Haukka, Ruslan E. Asfin, Peter M. Tolstoy, Vadim Yu. Kukushkin|2016|Phys.Chem.Chem.Phys.(PCCP)|18|14104|doi:10.1039/C6CP00861E
CCDC 1406017: Experimental Crystal Structure Determination
Related Article: Kalle Kolari, Joona Sahamies, Elina Kalenius, Alexander S. Novikov, Vadim Yu Kukushkin, Matti Haukka|2016|Solid State Sciences|60|92|doi:10.1016/j.solidstatesciences.2016.08.005
CCDC 1414621: Experimental Crystal Structure Determination
Related Article: Mikhail A. Kinzhalov, Alexander S. Novikov, Konstantin V. Luzyanin, Matti Haukka, Armando J. L. Pombeiro, Vadim Yu. Kukushkin|2016|New J.Chem.|40|521|doi:10.1039/C5NJ02564H
CCDC 1009208: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1009211: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1456509: Experimental Crystal Structure Determination
Related Article: Daniil M. Ivanov, Alexander S. Novikov, Galina L. Starova, Matti Haukka, Vadim Yu. Kukushkin|2016|CrystEngComm|18|5278|doi:10.1039/C6CE01179A
CCDC 1541822: Experimental Crystal Structure Determination
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1542913: Experimental Crystal Structure Determination
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1470271: Experimental Crystal Structure Determination
Related Article: Daniil M. Ivanov, Alexander S. Novikov, Galina L. Starova, Matti Haukka, Vadim Yu. Kukushkin|2016|CrystEngComm|18|5278|doi:10.1039/C6CE01179A
CCDC 1541821: Experimental Crystal Structure Determination
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1456075: Experimental Crystal Structure Determination
Related Article: Daniil M. Ivanov, Alexander S. Novikov, Galina L. Starova, Matti Haukka, Vadim Yu. Kukushkin|2016|CrystEngComm|18|5278|doi:10.1039/C6CE01179A
CCDC 1517184: Experimental Crystal Structure Determination
Related Article: Daniil M. Ivanov, Mikhail A. Kinzhalov, Alexander S. Novikov, Ivan V. Ananyev, Anna A. Romanova, Vadim P. Boyarskiy, Matti Haukka, Vadim Yu. Kukushkin|2017|Cryst.Growth Des.|17|1353|doi:10.1021/acs.cgd.6b01754
CCDC 1401549: Experimental Crystal Structure Determination
Related Article: Tatiyana V. Serebryanskaya, Alexander S. Novikov, Pavel V. Gushchin, Matti Haukka, Ruslan E. Asfin, Peter M. Tolstoy, Vadim Yu. Kukushkin|2016|Phys.Chem.Chem.Phys.(PCCP)|18|14104|doi:10.1039/C6CP00861E
CCDC 1541820: Experimental Crystal Structure Determination
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1509734: Experimental Crystal Structure Determination
Related Article: Daniil M. Ivanov, Mikhail A. Kinzhalov, Alexander S. Novikov, Ivan V. Ananyev, Anna A. Romanova, Vadim P. Boyarskiy, Matti Haukka, Vadim Yu. Kukushkin|2017|Cryst.Growth Des.|17|1353|doi:10.1021/acs.cgd.6b01754
CCDC 1009212: Experimental Crystal Structure Determination
Related Article: Xin Ding, Matti J. Tuikka, Pipsa Hirva, Vadim Yu. Kukushkin, Alexander S. Novikov, Matti Haukka|2016|CrystEngComm|18|1987|doi:10.1039/C5CE02396C
CCDC 1551262: Experimental Crystal Structure Determination
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569