Heterodinuclear Complexes Containing S2CPR3 as Asymmetric Bridges between Cobalt and Metals of Group 7 (Manganese, Rhenium) or Group 6 (Molybdenum, Tungsten): Selective Cobalt-Carbon Bond Formation. X-ray Structures of [MnCo(CO)5(.mu.-S2CPCy3)] and [MoCo(.eta.3-C3H5)(CO)4(.mu.-S2CPCy3)].cntdot.CH2Cl2

Reversible Isomerization via Migration of SnPh3 in S2CPCy3-Bridged Heterobinuclear Compounds. X-ray Structures of [(CO)3Re(μ-S2CPCy3)Mo(SnPh3)(CO)3] and [(CO)3(Ph3Sn)Re(μ-S2CPCy3)Mo(CO)3]

“…The S 2 CPR 3 ligand was found for the first time as a η 3 ;η 2 bridge in the symmetric template (CO) 3 Mn−Mn(CO) 3 1a. When it bridges two different metal fragments, M and M‘, two isomers can be expected, depending on which metal is bonded to the central carbon of the ligand.…”

“…During the last years we have developed synthetic routes to binuclear complexes with bridging η 3 ;η 2 -S 2 CPR 3 ligands . This bridge imparts a remarkable stability to the binuclear unit and, at the same time, rearranges facilely to adapt to changes in the molecule.…”

“…Interestingly, a definite preference for one of the isomers has been found in all the examples. For M = Mn(CO) 3 , M‘ = Re(CO) 3 , only isomer A (see Scheme ) is obtained either by reaction of [MnBr(CO) 3 (S 2 CPCy 3 )] with Na[Re(CO) 5 ] or by reaction of [ReBr(CO) 3 (S 2 CPCy 3 )] with Na[Mn(CO) 5 ] 1b. Therefore, with equal coordination sphere and oxidation states, the nature of the metal dictates the selective formation of the metal−carbon bond.…”

Potential Energy Surfaces for Mo + CO and W + CO

“…Organometallic complexes of molybdenum and tungsten have been the topic of many recent experimental studies. Investigation of such complexes and their properties could aid not only in our comprehension of catalysis and chemisorption but also in the area of organic chemistry and biochemistry, because those complexes play an important role in these areas, too. − The Mo−CO system has been employed as an oxidation and sulfidation agent and has thus attracted great attention. , Synthesis, structure, and properties of these complexes have been the topic of several studies. − Tungsten carbonyl species such as W(CO) 2 have been characterized by using the ultraviolet photoreduction method . The ground state of W(CO) + n ( n = 1−6) species have been studied theoretically at the ab initio level .…”

The formation and transformation of metallacycles containing phosphorus or sulfur on molybdenum– or tungsten–cobalt mixed-metal backbones ‡

“…The chemistry of heterobimetallic transition metal carbonyl complexes remains an area of continued interest. [1][2][3][4][5] The presence of two distinct metal centres within the same complex presents possibilities for the study of the relative reactivities of two different metal sites while cooperative interactions between the two metal centres may lead to complexes possessing unique reactivity properties.…”