Oxidation of Tricarbonylmolybdacarborane.3.?A New Entry to the First Examples of Sulfido-Bridged Dinuclear molybda(V)carboranes

Abstract

C 2 B 9 H 11 )Mo(CO) 3 ] 2 PPN 2 (2·PPN 2 ), a new precursor for the oxidative decarbonylation reaction, was synthesized in high yield by the one-electron oxidation reaction of [(C 2 B 9 H 11 )Mo(CO) 3 ]PPN 2 . 2·PPN2 was structurally characterized, showing a dimeric nature with long (3.321 Å) Mo-Mo bonding. Reaction of 2·PPN2 with sulfur gave the completely decarbonylated product [(C 2 B 9 H 11 )Mo(µ-S)(S)] 2 PPN 2 (3·PPN 2 ). The ligand substitution of the terminal sulfur ligands in 3·PPN2 to oxygen ligands was carried out with the use of PhIO to give [(C 2 B 9 H 11 )Mo(µ-S)(O)] 2 PPN 2 (4·PPN 2 ). The structures of 3·PPN2 and 4·PPN2 were also studied.

Oxidation of the Bis-molybdenum(0) Trianion [1,3,6-{Mo(CO)3}-3,6-(μ-H)2-1,1,1-(CO)3-2-Ph-closo-1,2-MoCB9H7]3-: Metal and Boron Vertex Substitution and Cluster Expansion

“…The {1,1,1-(CO) 3 -2-Ph- closo -1,2-MoCB 9 H 9 } 3- core in 1 is related to the long-known , molybdenum−dicarbollide species [1,2-R 2 -3,3,3-(CO) 3 - closo -3,1,2-MoC 2 B 9 H 9 ] 2- ( 2 ; R = H, Me, etc. ), whichalong with their 13-vertex analogues , similarly have a rich heterometallic chemistry. − It has already been noted 1 that some transition element fragments cause oxidation of 1 rather than giving bi- or trimetallic Mo(0)-containing species, and compounds 2 also readily undergo oxidation reactions to Mo II species and beyond. ,− We herein report upon the behavior of 1 upon oxidation with a variety of reagents, with these results detailing examples of cluster substitution at both metal and boron vertexes and also cluster expansion to yield molybdenum− di carbollide complexes.…”