LEWIS-BASEN ADDUKTE MONOMERER BIS(ETA(2)-ALKIN)AG(I)X-VERBINDUNGEN (X=BF4 ODER OSO2CF3)

The reaction of the organometallic 1,4-diyne Me(3)SiC=C-[Ti]-C=CSiMe(3 ) ([Ti] = (eta(5)-C(5)H(4)SiMe(3))(2)Ti) (1) with [AgX](n) (X = BF4 (2 a) or OSO2CF3 (2b)) affords {(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C=CSiMe(3)) (2)}AgX (X = BF4 (3a) or OSO2CF3 (3b)) with 85% yield. The (eta(2)-C=C SiMe(3))(2)AgX building block in 3 represents a 16-electron complex fr agment and the silver atom has a trigonal planar geometry. The reactio n of 3 with Lewis bases L leads to the formation of 5)-C(5)H(4)SiMe(3) )(2)Ti(C=CSiMe(3))(2)}Ag[(X)(L)] (L = THF; X = BF4 (4), (L = P(C=CPh)( 2)(CH(2)Ph); X = OSO2CF3 (5a)) (L = PPh(3); X = OSO2CF3 (5b)) (L = P(O Me)(3); X = OSO2CF3 (5c)) (L = N=CMe, X = BF4 (6a)) (L = N=CPh; X = BF 4 (6b)) (L = N=CPh; X = OSO2CF3 (6c)); with fumarodinitril [{[(eta(5)- (C=CSiMe(3))(2)]Ag}(2)(N=C-CH=CH-C=N)](OSO2CF3)(2) (7) is formed. Whi le 4-6 are 1:1 adducts of 3 and L, 7 has a 2:1 composition of 3 and N= C-CH=CH-C=N. The (eta(2)-C=CSiMe(3))(2)Ag[(X)(L)] building blocks in 4 -7 have an 18-electron count and the silver(I) coordination is pseudot etrahedral. All synthesized compounds have been characterized by analy tical and spectroscopic data (IR, H-1, C-13 and P-31 NMR and mass spec troscopy), and (5)H(4)SiMe(3))(2)Ti(C=CSiMe(3))(2)}Ag[(BF4)(THF)] (4) by X-ray analysis.