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Type: Artigo de periódico
Title: Synthesis and structural characterization of [Ir-4(mu-CO)(CO)(7){mu(4)-eta(3)-Ph2PC(H)C(Ph)PCBut}(mu-PPh2)]: Alkyne-phosphaalkyne coupling and formation of a novel 2-phosphabutadienylphosphine ligand
Author: Araujo, MH
Hitchcock, PB
Nixon, JF
Vargas, MD
Abstract: Reaction of [Ir-4(mu-H)(CO)(9)(Ph2PC=CPh)(mu-PPh2)] 1 with P drop CBut in CH2Cl2,at 35 degrees C for 4 h yields the novel compound [Ir-4(mu-CO)(CO)(7){mu(4)-eta(3)-Ph2PC(H)C(Ph)PCBut}(mu-PPh2)]2, which contains the 2-phosphabutadienylphosphine chain. Compound 2 is also formed upon thermolysis of [Ir-4(CO)(10)(Ph2PC=CPh)(PPh2H)] 3 in the presence of P=CBut in hf, at 40 degrees C, for 48 h. Small amounts of [Ir-4(mu-CO)(CO)(7)(mu(3)-eta(2)-HCCPh)(mu-PPh2)(2)] 4 are always obtained from both reactions, because of the competing rates of the transformations of 1 and 3 into 4 and of their reactions with P=CBut. Compound 2 was characterized by analytical and spectroscopic studies such as FAB ms, H-1 (PC)-P-31-C- 13, 2D P-31-H-1 HETCOR, nOe difference and DEFT NMR experiments, which led to its formulation and established the coupling between the coordinated Ph2PC=CPh and PCBut and the migration of the hydride to the C alpha of the (PhPC)-P-2=CPh ligand. However, it was impossible to establish unambiguously if cleavage of the P-C-sp bond of the Ph2PC=CPh ligand had occurred and the mode of interaction of the organophosphorus chain. An X-ray diffraction study of compound 2 established a butterfly arrangement of iridium atoms with the new ligand interacting with the metal framework via four sigma bonds and the PPh2 phosphorus lone pair.
Subject: iridium cluster
coupling reaction
Country: Brasil
Editor: Soc Brasileira Quimica
Rights: aberto
Date Issue: 1998
Appears in Collections:Unicamp - Artigos e Outros Documentos

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