SYNTHESIS AND REACTIVITY OF FUNCTIONALIZED DIMETHYLSILYL COMPLEXES OF THE FORMULA (ETA-5-C5H5)RE(NO)(PPH3)(SIME2X) - NEW BASE-STABILIZED SILYLENE COMPLEXES, NOVEL LEWIS ACID ADDUCTS, AND EVIDENCE FOR BASE-FREE SILYLENE COMPLEXES
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Reactions of (5C5H5)Re(NO)(PPh3)(SiMe2H) (1) and CHCl3, CBr4, and CHI3 give halosilyl complexes (5C5H5)Re(NO)(PPh3)(SiMe2X) [X = Cl (2), Br (3), I (4); 6684%]. Addition of Me3SiOTf to 2 gives triflate (5C5H5)Re(NO)(PPh3)(SiMe2OTf) (5; 97%), which in turn reacts with (Me2N)3S [SiMe3F2] to give (5C5H5)Re(NO)(PPh3)(SiMe2F) (6; 77%). Reaction of 5 and pyridine gives the basestabilized silylene complex [(5C5H5)Re(NO)(PPh3){SiMe2(NC5H5)}] TfO (7; 84%). CH2Cl2 solutions of (5C5H5)Re(NO)(PPh3)(CH3) (8) or 2 and Lewis acids are studied by IR and NMR. As assayed by IR, 8/ECl3 solutions (E = B, Al) show ReNOECl3 (major) and ReECl3 (minor) adducts. Solutions of 2/BCl3 show analogous adducts (78C), and in the presence of excess BCl3 (5C5H5)Re(NOBCl3)(PPh3)(SiMe2Cl) (11) crystallizes. Solutions of 2/AlCl3 show uncomplexed 2 and ReAlCl3 (major) and ReNOAlCl3 (minor) adducts. In contrast to 27 and 2/BCl3, 1H and 13CNMR spectra of 2/AlCl3 suggest an equilibrium with the basefree silylene complex [(5C5H5)Re(NO)(PPh3)( = SiMe2)] X. Copyright 1991 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim
