Sulfur bridged binuclear complexes

Binuclear palladium(II) complexes of dppm may also be prepared by oxidation, for example of [ClPd(ju-dppm)2PdCl] with S8 to give the sulfur-bridged A-frame molecule [Pd2Cl2(]U-S)(ju-dppm)2], or of [Pd2( -dppm)3] with CHRX2 to give the A-frame [Pd2X2(jU-CHR)(/t-dppm). 68... 

Dithiolenes can serve quite well as bridging ligands (see compound 43). A regular dithiolene ligand has also been shown to coexist in a binuclear complex with a bridging one the sulfur rich dithiolene28 Mo2(S2)(S2C2Ph2)4, cited earlier in a different context, is an example of this type of coexistence. 

Sulfur ligands, 633-655 coordination ability, 516 Sulfur monoxide metal complexes instability, 636 Superoxide dismutase, 773 copper complexes, 772 Superoxo complexes, 315-330 binuclear, 323, 325 reactions, 330 bridged... 

Electron transfers may lead to modifications of the metal-sulfur core of binuclear sulfur-bridged complexes. The CV of [M2S2(cp )2(/i-S)2] 11 (M = Mo or W, cp = /j-CsHs nMe,) [30] showed that the first reduction was a one-electron process. 

Binuclear complexes with bridging sulfur compounds result from the following reactions ... 

Although considerable effort has gone into the preparation and structural determination of sulfur-containing copper complexes, definitive characterization of binuclear complexes containing a mercaptide bridge has proved exceedingly difficult. Two major problems which manifest this difficulty are the tendency for Cu(II) to readily oxidize mercaptans... 

None of the metal-metal bonds shown on the binuclear complexes in Figure 5.20 undergoes facile insertion of small molecules. For example (/Lt-Ph2Ppy)2Pd2Cl2, which is isoelectronic with (/Lt-dpm)2Pd2Cl2, does not react with carbon monoxide or sulfur dioxide. This lack of reactivity has been attributed to the limitations that the bridging Ph2Ppy places on the... 

Harrop TC, Olmstead MM, Mascharak PK (2004) Structural models of the bimetallic subunit at the A-cluster of acetyl coenzyme a synthase/CO dehydrogenase binuclear sulfur-bridged Ni-Cu and Ni-Ni complexes and their reactions with CO. J Am Chem Soc 126 14714—14715... 

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