Insertion of heteroallenes into the rhenium-hydride bond

Dithioformato [Re{eta(2)-SC(H)S}(NO)P-3]BPh4 (1), thioformamido [Re{eta(2)-RNC(H)S}(NO)P-3]BPh4 (2) (R = Et, p-tolyl), form-amido [Re{eta(2)-PhNC(H)O}(NO)P-3]BPh4 (3) and formamidinato [Re{eta(2)-p-tolylNC(H)Np-tolyl}(NO)P-3]BPh4 (4) (P = PPh2OEt) complexes were prepared by allowing the hydride ReH2(NO)P-3 to react first with triflic acid and then with the appropriate heteroallene CS2, RNCS, PhNCO and p-tolyINCNp-tolyl. Treatment of the ReH2(NO)L(PPh3)(2) [L = P(OEt)(3), PPh(OEt)(2)] and ReH2(NO) (PPh3)(3) hydrides first with triflic acid and then with isothiocyanate RNCS (R = Et, p-tolyl) gave the [Re{eta(2)-RNC(H)S}(NO) {P(OEt)(3)}(PPh3)(2)]BPh4 (5, 6) and [Re(eta(2)-RNC(H)S)(NO)(PPh3)(3)]BPh4 (7) derivatives. Depending on the nature of the phosphite, instead, the reaction of ReH2(NO)L(PPh3)(2) and ReH2(NO)(PPh3)(3) hydrides first with CF3SO3H and then with isocyanate RINCO (R1 = Ph, p-tolyl) gave the chelate [Re{eta(2)-R1NC(H)O}(NO){P(OEt)(3)}(PPh3)(2)]BPh4 (8) and [Re{eta(2)-RINC(H)O} (NO)(PPh3)(3)]BPh4 (10) complexes with P(OEt)(3) or PPh3, while the eta(1)-coordinate [Re{eta(1)-RNC(H)S}(NO){PPh(OEt)(2)}(2)(PPh3)(2)]BPh4 (9) derivative was obtained with the PPh(OEt)(2) phosphite ligand. eta(1)-Coordinate dithioformato [Re{eta(1)-SC(H)=S}(NO) {PPh(OEt)(2)}(2)(PPh3)(2)]BPh4 (11) and formato [Re{eta(1)-OC(H)=O}(NO){PPh(OEt)(2)}(2)(PPh3)(2)]BPh4 (12) complexes, as well as the formamidinato [Re{eta(2)-p-tolylNC(H)Np-tolyl}(NO){P(OEt)(3)}(PPh3)(2)]BPh4 (13) derivative were also prepared. (c) 2005 Elsevier B.V. All rights reserved.