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Syntheses, reactions, and structures of dioxycarbene complexes of rhenium

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00258a012· OSTI ID:6371312

The cyclic dioxycarbene complex Re(CO)4Br(COCH2CH2O) (I) reacts with PPh3 to give initially fac-Re(CO)3(PPh3)Br(COCH2CH2O) (II) and upon further reaction Re(CO)2(PPh3)2Br(COCH2CH2O) (II). The reaction of I with the diphosphines Ph2P(CH2)/sub n/PPh2 (n = 1,2) gives the diphosphine-bridged complexes (Re(CO)3Br(COCH2CH2O))2(Ph2P(CH2)/sub n/PPh2) (IV, n = 1; V, n = 2). The structures of I and V were established by X-ray diffraction studies. The crystals of I are orthorhombic, space group Pbca, with a = 11.764 (2) A, b = 17.579 (4) A, c = 10.658 (2) A, and Z = 8, while those of V are triclinic, space group P anti I, with a = 11.160 (2) A, b = 11.369 (3) A, c = 10.090 (3) A, = 111.58 (3), US = 95.40 (2), el = 92.78 (2), Z = 1, and two acetones ((CH3)2CO) of crystallization. The dimethyldithiocarbamate ion, S2CN(CH3)2, reacts with I to remove in effect ethylene oxide form the carbene ligand, giving Gr(CO)5Br and HOCH2CH2SC(=S)N(CH3)2.

Research Organization:
Iowa State Univ., Ames
DOE Contract Number:
W-7405-ENG-82
OSTI ID:
6371312
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:11; ISSN INOCA
Country of Publication:
United States
Language:
English