OXYGEN ATOM TRANSFER FROM A PHOSPHINE OXIDE TO TUNGSTEN(II) COMPOUNDS

被引:35
作者
BROCK, SL [1 ]
MAYER, JM [1 ]
机构
[1] UNIV WASHINGTON,DEPT CHEM,SEATTLE,WA 98195
关键词
D O I
10.1021/ic00009a034
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
WCl2(PMePh2)4 (1) reacts rapidly with Ph2P(O)CH2CH2PPh2 (5, the monooxide of diphos) to give an adduct, WCl2[Ph2P(O)CH2CH2PPh2](PMePh2)2 (6). On being heated at 80-degrees-C for 8 h, 6 rearranges by transferring the phosphoryl oxygen to tungsten, with the formation of tungsten-oxo complexes W(O)Cl2(diphos)(PMePh2) (7) and W(O)Cl2(PMePh2)3 (2), as well as WCl2(diphos)(PMePh2)2 (8). This is the first example of oxygen atom transfer from a phosphine oxide to a metal center, a remarkable reaction because of the strength of the P-O bond (roughly 130 kcal/mol). The presence of an oxygen atom transfer step in this reaction has been confirmed by oxygen-18-labeling studies. WCl2(PMe3)4 (9) also deoxygenates 5, forming similar tungsten-oxo complexes, but in this case an intermediate is not observed. Nonchelating phosphine oxides are unreactive with 1 and 9, indicating that the chelating nature of 5 is needed to assist the initial coordination of the phosphoryl oxygen. The kinetic barriers to deoxygenation of phosphine oxides lie both in the initial coordination of the phosphine oxide and in the actual oxygen atom transfer step. Allyl- and vinylphosphine oxides also react with 1, but oxygen atom transfer from these substrates has not been observed. An unusual tungsten-oxo complex with a chelating allyldiphenylphosphine oxide, W(O)Cl2[CH2=CHCH2P(O)Ph2]PMePh2 (13) has been isolated and its X-ray crystal structure determined. Crystal data for 13: a = 9.2547 (9) angstrom, b = 16.738 (2) angstrom, c = 18.023 (2) angstrom, beta = 100.696 (9)-degrees, monoclinic, P2(1)/c, Z = 4.
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页码:2138 / 2143
页数:6
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共 42 条
[1]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[2]  
ATAGI LM, UNPUB
[3]  
Bakar M. A., 1989, J CHEM SOC DA, P1417
[4]   COMMUNICATION - THE 1ST EXAMPLES OF TRIPHENYLPHOSPHINEOXIDE AND TRIPHENYLPHOSPHINESULFIDE 7-COORDINATE COMPLEXES OF MOLYBDENUM(II) AND TUNGSTEN(II) [J].
BAKER, PK ;
KENDRICK, DA .
JOURNAL OF COORDINATION CHEMISTRY, 1988, 17 (04) :355-358
[5]   POLY(DIPHENYLVINYLPHOSPHINE OXIDE) [J].
BERLIN, KD ;
BUTLER, GB .
JOURNAL OF ORGANIC CHEMISTRY, 1961, 26 (07) :2537-&
[6]   OXIDATIVE ADDITION OF CARBON OXYGEN AND CARBON NITROGEN DOUBLE-BONDS TO WCL2(PMEPH2)4 - SYNTHESIS OF TUNGSTEN METALLAOXIRANE AND TUNGSTEN OXO-ALKYLIDENE AND IMIDO ALKYLIDENE COMPLEXES [J].
BRYAN, JC ;
MAYER, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (06) :2298-2308
[7]   OXIDATIVE ADDITION OF CARBON-DIOXIDE, EPOXIDES, AND RELATED MOLECULES TO WCL2(PMEPH2)4 YIELDING TUNGSTEN(IV) OXO, IMIDO, AND SULFIDO COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURE OF W(O)CL2(CO)(PMEPH2)2 [J].
BRYAN, JC ;
GEIB, SJ ;
RHEINGOLD, AL ;
MAYER, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (09) :2826-2828
[8]   OXYGEN ATOM TRANSFER BETWEEN RHENIUM, SULFUR, AND PHOSPHORUS - CHARACTERIZATION AND REACTIVITY OF RE(O)CL3(ME2S)(OPPH3) AND RE(O)CL3(CNCME3)2 [J].
BRYAN, JC ;
STENKAMP, RE ;
TULIP, TH ;
MAYER, JM .
INORGANIC CHEMISTRY, 1987, 26 (14) :2283-2288
[9]   TERTIARY PHOSPHINE AND ARSINE COMPLEXES OF TUNGSTEN(IV) [J].
BUTCHER, AV ;
CHATT, J ;
RICHARDS, PL ;
LEIGH, GJ .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1972, (10) :1064-&
[10]   SOME TRIMETHYL PHOSPHINE AND TRIMETHYL PHOSPHITE COMPLEXES OF TUNGSTEN(IV) [J].
CARMONA, E ;
SANCHEZ, L ;
POVEDA, ML ;
JONES, RA ;
HEFNER, JG .
POLYHEDRON, 1983, 2 (08) :797-801