Synthesis and crystal structure analysis of ferrocenylthiosemicarbazone complexes of palladium(II): Unusual σPd–C bond cleavage

Abstract

The reaction of the thiosemicarbazones (η 5-C 5H 5)Fe(η 5-C 5H 4)C(H) NN(H)C( S)NHR (R = H, a; R = Me, b) with K 2PdCl 4 afforded octanuclear cyclometallated complexes [Pd{(η 5-C 5H 5)Fe(η 5-C 5H 3)C(H) NN C(S)NHR}] 4 (R = H, 1a; R = Me, 1b). Reaction of complexes 1a and 1b with tertiary diphosphines in 1:2 molar ratio and subsequent recrystallization from CH 2Cl 2/ n-C 6H 14 gave rise to tetranuclear complexes [{Pd[(η 5-C 5H 5)Fe(η 5-C 5H 4)C(H) NN C(S)NHR](Cl)} 2(μ-Ph 2P(CH 2) n PPh 2)] (R = H, n = 4, 2a; R = Me, n = 1, 2b; n = 4, 3b). Treatment of complexes 1a and 1b with tertiary monophosphines in 1:4 molar ratio and subsequent recrystallization from CH 2Cl 2/ n-C 6H 14 gave rise to dinuclear complexes [Pd{(η 5-C 5H 5)Fe(η 5-C 5H 4)C(H) NN C(S)–NHR}(Cl)(P)] (R = H: P = PPh 3, 3a; P = PPh 2Et, 4a; P = P(C 6D 5) 3, 5a; R = Me: P = PPh 3, 4b; P = PPh 2Et, 5b; P = P(C 6D 5) 3, 6b). The crystal structures of 2a and 2b have been determined by X-ray crystallography.