Reduction of Main Group Oxides via Metal Carbonyls and Carbonylate Anions

Reduction of Main Group Oxides via Metal Carbonyls and Carbonylate Anions 

Metal-bound isocyanates give similar results to nitrosyl compounds.363,367 Starting with [Ru4(NCO)(CO)13] , one can obtain [Ru4(CO)i2N] in 78% yield upon thermolysis. Treatment of [Ru2(CO)r(NCO)] (x = 10,11) with Ru3(CO),2 leads to the hexanuclear nitride [Ru6(CO)i6N] in 82% yield. Organic nitroso and nitro can be similarly reduced by metal carbonyls or carbonylate anions. These reactions are discussed in the later section on reactions with organic substrates. 

The deoxygenation reactions of As, Sb, and Bi oxides are known as well. A number of examples are given in Eqs. (123)-(131).73,33 136,231 233,4°5 Equation (131) is noteworthy in that it produces a heteromain group li- 

Addition of an electron pair (reduction) or ligand can result in M-M bond breakage, whereas removal of an electron pair (oxidation) or ligand can result in M-M bond formation. The most common form of this reactivity pattern is the elimination of CO induced either thermally or photochemi-cally. In the case of E[ML ]3 complexes, intermediates with only one or two M-M bonds are often not observed, and the resultant complexes are the doxo-tetrahedral complexes as exemplified in Eqs. (141)65,139 and 

The Fe3(CO)10 xLrPR (28 x = 1-3) system is especially flexible in its ability to add and subtract ligands. Stepwise addition occurs to give complexes with two and one M-M bond(s). These reactions are reversible so that substituted derivatives of each of the compound types can be obtained  

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