REACTIVITY OF ALKYNYL-SUBSTITUTED PHOSPHI NITES AND PHOSPHANES - COPPER(I) AND SILVER(I) TRIFLUOROMETHANE SULFONATES

The reaction of (R(1))(R(2))(PhC=C)P (1a: R(1) = 2,4,6-(t)Bu(3)C(6)H(2 )O, R(2) = NEt(2); 1b: R(1) = Ph, R(2) = C = CPh; 1c: R(1) = R(2) = C = CPh) with [M(I)OSO(2)CF(3)] (2: M = Cu, 3: M = Ag) affords the dimer ic complexes {[(R(1))(R(2))(PhC=C)P]M(I)(mu-OSO2CF3)}(2) (4a: M = Cu, R(1) = 2,4,6-(t)Bu(3)C(6)H(2)O, R(2) = NEt(2); 4b: M = Cu, R(1) = R(2) = C = CPh; 5a: M = Ag, R(1) = 2,4,6-(t)Bu(3)C(6)H(2)O, R(2) = NEt(2); 5b: M = Ag, R(1) = Ph, R(2) = C = CPh; 5c: M = Ag, R(1) = R(2) = C = CPh) in yields between 86 and 97%. In 4 and 5 each (R(1))(R(2))(PhC=C) P building block is datively bonded to a M(I)OSO(2)CF(3) unit. By the formation of M(I)OSO(2)CF(3)M(I) bridges (M = Cu, Ag) dimers are forme d. The X-ray structure analysis of 5a is reported. Crystals of 5a are monoclinic, space group P2(1)/n with cell constants a = 1722.3(5), b = 1099.2(4), c = 1884.5(6) pm, beta = 107.21(2)degrees, V = 3409(2) X 1 0(6) pm(3) and Z = 2.