O-ATOM TRANSFER-REACTIONS IN SOME MANGANESE AND RHENIUM CARBONYL-COMPOUNDS

The compounds M(CO)5Cl (M = Mn (1a); M = Re (1b)) undergo reaction wit h (CH3),NO in CH2Cl2 to produce the series of anionic derivatives [M(C O)4L2]1- (M = Mn (2a); M = Re (2b); L - Cl or N(CH 3)3), [Mn(CO)3Cl3]2 - (3a) and [Mn2(CO)6(mu2-Cl)3]-(4a). These products have been identifi ed from a comparison of their IR spectroscopic properties with authent ic samples prepared by the direct reaction of Mn(CO)5Cl with Et4NCl. T he PPN+ salt of 4a has been characterized by X-ray crystallography. Th e compound crystallizes in the monoclinic space group P2(1)/n with the following cell dimensions; a = 9.5335(12), b = 15.6246(19) and c = 29 .158(6) angstrom; beta = 92.369(16). Further reactions of the intermed iate manganese chloride complexes with PPNNO2 in CH2Cl2 lead to the fo rmation of the series of anionic derivatives [Mn(CO)3Cl2(NO2)]2- (5a), [Mn(CO)3Cl(NO2)2]2- (6a), [M(CO)3(NO2)2(ON(O))]2- (7a) and upon cryst allization the trimer [Mn3(CO)6(mu2-NO(O))4(mu2-O(NO))2]2- (8a). React ion of Re(CO)5Cl with PPNNO2 in CH2Cl2 in the absence of Me3NO yields the anionic species [Re(CO)3(NO2)2(ONO)]2- (7b), whereas in tetrahydro furan under the same conditions the dianion [fac-Re(CO)3(ONO)3]2- (9b) is formed. Both compounds have been characterized as their PPN+ salts by X-ray structure analysis. Compound 7b has been shown to exist in t he monoclinic space group P2(1)/n with the following cell dimensions: a = 10.728(5), b = 13.231(3) and c = 23.383(7) angstrom; beta = 100.58 (3). Complex 9b crystallizes in the orthorhombic space group Pbca; the cell dimensions are a = 16.931(12), b = 19.593(9) and c = 19.971(13) angstrom.