Reactions between metal carbonyl anions and cations: rapid two-electron transfer followed by one-electron back transfer

Hydride Participation in Electron Transfer Processes between Metal Carbonyl Anions and Cations

“…Reactions between metal carbonyl anions and cations, which effect CO transfer, have been reported by Zhen and Atwood . The transfer is a synchronous two-electron transfer and CO transfer in the opposite direction.…”

Cleavage of sulfur dioxide on (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)2 to form S8 and a thiosulfate complex (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)(.mu.-SSO3). Possible role in homogeneous hydrogenation of sulfur dioxide catalyzed by molybdenum-sulfur complexes

“…Only a small amount of presumably the SS1602180 isotopomer was present, as indicated by a weak vso band at 992 cm"1. The absence of significant lsO-labeled 2 showed that formation of 2 occurred via amine-promoted disproportionation of S02 (eq 3) rather than the 1802 oxidation pathway (eq 4), presumably because the rate of eq 3 is much faster than eq 4 under these conditions. This further confirms that oxygen from 02 does not become incorporated into the thiosulfate ligand and provides a check that isotopic exchange of l802 and S02 is not occurring prior to any reaction with 1.…”

“…Molecular geometry and atom-labeling scheme for *2 2(µ-82)(µ-8)(µ-8803) (2; 35% ellipsoids). H2 is complete within 4 h if amine (~3% of solvent volume) is present but otherwise is incomplete after days. [Cp*MoS(SH)]2 is the final product if excess H2 is present, but NMR shows that 1 is formed initially and is converted to the SH complex during the course of the reduction.…”

Reaction of [PPN][Fe3(CO)CCOC(O)CH3] with the Metal Nucleophile [Re(CO)5]- To Generate a Mixed-Metal Acetylide, [PPN][Fe3(CO)9CCRe(CO)5]

“…Solvents were prepurified by distillation from drying agents (CH 2 Cl 2 from P 2 O 5 ; THF and Et 2 O from sodium/benzophenone; i -PrOH from Mg/I 2 ) and were stored under N 2 until needed. Published syntheses were used to prepare [PPN] 2 [Fe 3 (CO) 9 CCO], [PPN][Fe 3 (CO) 9 CCOC(O)CH 3 ], and [PPN][Re(CO) 5 ] …”