0000000000505576
AUTHOR
Oscar Tutusaus
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…
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.
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…
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…