Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 100. Synthesis of mixed-metal compounds via the salts [NEt₄][Rh(CO)L(η⁵-C₂B₉H₉R₂)](L = PPh₃, R = H; L = CO, R = Me); crystal structures of the complexes [WRhAu(µ-CC₆H₄Me-4)(CO)₃(PPh₃)(η-C₅H₅)(η⁵-C₂B₉H₁₁)] and [WRh₂Au₂

Abstract

The rhodacarbaborane salts (I) and (IV) are used to prepare the mixed‐metal complexes (III), (V), (VII), and (VIII).

Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 101. Synthesis of the compounds [WPt(µ-CC6H4Me-4)(µ-σ:ηx-C2BnHn–1Me2)(CO)2(PMe2Ph)2](x= 5, n= 9; x= 6, n= 10); crystal structures of an isomer of each complex

“…The tungsten atom in compound (7a) carries two terminally bound CO groups, and as expected the platinum the two PMe,Ph ligands. The alkylidyne moiety asymmetrically bridges the metal-metal bond [W-C(7) 1.89 (1) and Pt-C(7) 2.14(1) A].…”

“…The structure of one isomer of the dimetal compound was determined by X-ray diffraction. The W-Pt bond [2.720 (1) A] isspanned by thep-tolylmethylidyne group [W-p-C 1.89 (1), Pt-p-C 2.14 (1) 81 and by a C,Bg fragment. The latter is co-ordinated to the W atom via the open pentagonal face of the nido-icosahedral cage, and bridges to the Pt atom through an exopolyhedral B-Pt 0 bond [2.17 (1) A].…”

“…The W-Pt bond [2.720 (1) A] isspanned by thep-tolylmethylidyne group [W-p-C 1.89 (1), Pt-p-C 2.14 (1) 81 and by a C,Bg fragment. The latter is co-ordinated to the W atom via the open pentagonal face of the nido-icosahedral cage, and bridges to the Pt atom through an exopolyhedral B-Pt 0 bond [2.17 (1) A]. This boron atom is in the p site with respect to the carbon atoms in the b B B C e ring.…”

“…The W-Pt bond [2.738(1) A] is bridged by the alkylidyne group [W-p-C 1.92(1), Pt-p-C 2.14(1) A] and by a C,Blofragment. The non-planar latter is q6 co-ordinated to the tungsten, but the cage also forms a B-Pt CJ bond [2.15 ( 1 ) A]. This linkage involves a boron atom of the B, group to a carbon, and correspondingly the other isomer face of the is assigned a structure in which it is the c B C B B 8 atom of the hexagonal ring which bonds to platinum.…”

“…X 2 610(1) 4 165(1) 2 287(3) 1 199(3) 7 256 (8) 5 796 (8) 3 996 (9) 4081 (11) 4 856 (12) 4 264 ( 10) 5 068 (13) 5 260 ( 14) 5 114(13) 6 130 (12) 6 898(13) 6 349(13) 6 385 (14) 6 033( 1 1) 5 917 (10) 6 565(12) 6 400( 13) 4 104 (11) 4 122 (11) 2 667 ( 10) Y 1 536(1) 1 104(1) 2 220 ( 1) 999(1) 1 224 (4) 505( 4) 898(5)…”