Chlorocarbonyl-1,2-bisdiphenylphosphino-1,2-dicarbadodecaboranerhodium(I) and chloro-1,2-bisdiphenylphosphino-1,2-dicarbadodecaboranetriphenyl-phosphinerhodium(I): Preparation and catalytic properties

1,2-Bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane

“…Owing to their interesting chemical and physical properties, organic or organo-element derivatives of dicarba-closo-dodecaboranes have received much attention during the past few decades. These types of compounds can be used as catalysts (Hart & Owen, 1985;Longato & Bresadola, 1982), as precursors for ceramic materials (Hsu et al, 1991) and in medical areas (Hawthorne, 1993;Gielen et al, 1995). 1,2-Dicarba-closo-dodecaborane is an icosahedral cluster with two C atoms in adjacent positions.…”

Rhodium Complexes with the New Anionic Diphosphine [7,8-(PPh2)2-7,8-C2B9H10]-Ligand

“…12 The [Rh{7,8-(PPh 2 ) 2 -7,8-C 2 B 9 H 10 }(cod)] molecule exhibits rotational disorder in the cod ligand positions, the two groups of cod atoms being labeled C(51)-C(58) (conformer 1) and C(61)-C(68) (conformer 2) (C(51)-C(58) (pop ) 0.6852) and C(61)-C(68) (pop ) 1 -0.6852)) (see Figure 1). The average geometry for the rhodium atom is approxi-mately square planar, the average P-RhsCdC angle being 94.62°, CdCsRhsCdC being 86.34°, and P(1)-Rh-P(2) being 85.33(3)°and the rhodium atom lies within the plane described by the atoms P(1), P(2), C (7), and C (8). In contrast, a copper complex with the same [7,8-(PPh 2 ) 2 -7,8-C 2 B 9 H 10 ] -ligand involves coordination of the metal atom at an angle of 20.4°to the plane of the P(1), P(2), C(7), C(8) atoms, 13 allowing a distorted tetrahedral coordination environment for the copper atom.…”

“…7 The catalytic properties of rhodium complexes based on the neutral closo-carboranyldiphosphines have also been noted. 8 As a consequence, the eclipsed anionic diphosphine [7,8-(PPh 2 ) 2 -7,8-C 2 B 9 H 10 ] -was synthesized and structurally characterized to understand the influence of the ligand's negative charge on the P-Rh bonds, without the interference of other charge-compensating anionic ligands. 5 Here we report the synthesis of Rh(I) complexes based on the eclipsed anionic diphosphine [7,8-(PPh 2 ) 2 -7,8-C 2 B 9 H 10 ] -.…”

“…These complexes are catalytically active in the hydrogenation of olefins, including stereoselective hydrogenation . The catalytic properties of rhodium complexes based on the neutral closo -carboranyldiphosphines have also been noted …”

Reactions and Coordination Properties of the First Secondary Carbaboranyldiphosphane: 1,2-Bis(phenylphosphanyl)-1,2-dicarba-closo-dodecaborane(12)

“…The mixture of stereoisomers of 1a, b reacts with CuCl in THF to give rac-and meso-[CuCl(THF){1,2-Organo-element and organic derivatives of dicarba-closododecaboranes(12) have received increasing attention during the last decade due to their interesting chemical and physical properties. Thus, these compounds have been employed as catalysts [1] [2] , as doping reagents in semiconductor materials [3] , as precursors for ceramic materials [4] , and in medical areas [5] [6] [7] . Hence applications in medicine can be envisioned for related carbaboranylphosphanes and their transition-metal complexes [8] .…”