Insertion of heteroallenes into the rhenium-hydride bond

Dithioformato Re{η²-SC(H)S}(NO)P₃]BPh₄ (1), thioformamido Re{η²-RNC(H)S}(NO)P₃]BPh₄ (2) (R = Et, p-tolyl), formamido Re{η²-PhNC(H)O}(NO)P₃]BPh₄ (3) and formamidinato Re{η²-p-tolylNC(H)Np-tolyl}(NO)P₃]BPh₄ (4) (P = PPh₂OEt) complexes were prepared by allowing the hydride ReH₂(NO)P₃ to react first with triflic acid and then with the appropriate heteroallene CS₂, RNCS, PhNCO and p-tolylNCNp-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{η²-RNC(H)S}(NO){P(OEt)₃}(PPh₃)₂]BPh₄ (5, 6) and Re(η²-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 R1NCO (R1 = Ph, p-tolyl) gave the chelate Re{η²-R1NC(H)O}(NO){P(OEt)₃}(PPh₃)₂]BPh₄ (8) and Re{η²-R1NC(H)O}(NO)(PPh₃)₃]BPh₄(10) complexes with P(OEt)₃ or PPh₃, while the η¹-coordinate Re{η¹-RNC(H)S}(NO){PPh(OEt)₂}₂(PPh₃)₂]BPh₄ (9) derivative was obtained with the PPh(OEt)₂ phosphite ligand. η¹-Coordinate dithioformato Re{η¹-SC(H)S}(NO){PPh(OEt)₂}₂(PPh₃)₂]BPh₄ (11) and formato Re{η¹-OC(H)O}(NO){PPh(OEt)₂}₂(PPh₃)₂]BPh₄ (12) complexes, as well as the formamidinato Re{η²-p-tolylNC(H)Np-tolyl}(NO){P(OEt)₃}(PPh₃)₂]BPh₄ (13) derivative were also prepared.