Effect of ligand variation on the site of protonation in the metal carbynes CpL2MoCBu and TpL2MoCBu [L = CO, P(OR)3]

被引：11

作者：

Torraca, KE ^{[1
]}

Ghiviriga, I ^{[1
]}

McElwee-White, L ^{[1
]}

机构：

[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA

来源：

ORGANOMETALLICS | 1999年 / 18卷 / 11期

关键词：

D O I：

10.1021/om990047x

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The site of thermodynamic protonation of the Fischer carbynes CpL2Mo=CBu and TpL(2)Mo=CBu [L = CO, P(OR)(3)] with HBF4 depends on the number of pi-acid CO ligands. As the number of carbonyls increases from zero to two and the electron density at the metal center is decreased by back-bonding, the protonation site shifts from the metal to the carbyne carbon. Parallel behavior in the Tp and Cp series of complexes allows the change in protonation site to be attributed to electronic effects in the ancillary ligands.

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页码：2262 / 2266

页数：5

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共 34 条

[11] AN AGOSTIC MU-METHYNE MOLYBDENUM IRON COMPLEX FROM PROTONATION OF A MU-CARBIDE PRECURSOR, TP'(CO)2MO=CFE(CO)2CP [J].

ETIENNE, M ;

WHITE, PS ;

TEMPLETON, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (06) :2324-2325

[12] THE MECHANISM OF PROTONATION OF CARBYNE COMPLEXES - X-RAY CRYSTAL-STRUCTURES OF [HMO(CCH2BUT)(P(OME)3)2(ETA-C5H5)][BF4] AND [MO(CF3CO2)(CF3CO2H)(P(OME)3)2(ETA-C5H5)] [J].

GREEN, M ;

ORPEN, AG ;

WILLIAMS, ID .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1982, (09) :493-495

[13] A TUNGSTEN T-SHAPED METHYLENE COMPLEX AND RELATED METHYLIDYNE HYDRIDE COMPLEXES [J].

HOLMES, SJ ;

SCHROCK, RR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (15) :4599-4600

[14] MULTIPLE METAL-CARBON BONDS .26. ALPHA-HYDRIDE ELIMINATION FROM METHYLENE AND NEOPENTYLIDENE LIGANDS - PREPARATION AND PROTONATION OF TUNGSTEN(IV) METHYLIDYNE AND NEOPENTYLIDYNE COMPLEXES [J].

HOLMES, SJ ;

CLARK, DN ;

TURNER, HW ;

SCHROCK, RR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (23) :6322-6329

[15] MULTIPLE METAL-CARBON BONDS .33. SOME REACTIONS OF TUNGSTEN METHYLIDYNE COMPLEXES AND THE CRYSTAL-STRUCTURE OF [W2(CPME3)2(PME3)4CL4][ALCL4]2 [J].

HOLMES, SJ ;

SCHROCK, RR ;

CHURCHILL, MR ;

WASSERMAN, HJ .

ORGANOMETALLICS, 1984, 3 (03) :476-484

[16] PROTONATION OF THE ALKYLIDYNETUNGSTEN COMPLEXES [W(CR)(CO)2(ETA-C5H5)] (R = C6H4ME-2, C6H3ME2-2,6 OR C6H4OME-2) [J].

HOWARD, JAK ;

JEFFERY, JC ;

LI, S ;

STONE, FGA .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (04) :627-634

[17] PROTON-INDUCED DIMERIZATION AND RELATED REACTIONS OF MONONUCLEAR TUNGSTEN CARBYNE COMPLEXES - CRYSTAL-STRUCTURES OF THE COMPOUNDS [W(=C(H)(C6H4ME-4)]-(I)(CO)2(ETA-C5H5)] AND [W(ETA-2-C2(OH)(C6H4ME-4)](CO)(PME3)(ETA-C5H5)][BF4].(ME2CO) [J].

HOWARD, JAK ;

JEFFERY, JC ;

LAURIE, JCV ;

MOORE, I ;

STONE, FGA ;

STRINGER, A .

INORGANICA CHIMICA ACTA-ARTICLES AND LETTERS, 1985, 100 (01) :23-32

[18] PROTONATION OF THE ALKYLIDYNETUNGSTEN COMPLEX [W(CC6H4CH2OME-2)(CO)2(ETA-C5H5)] [J].

JEFFERY, JC ;

LI, S ;

STONE, FGA .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (04) :635-640

[19] SYNTHESIS OF ALKYLIDYNE TUNGSTEN COMPLEXES WITH HYDROTRIS(PYRAZOL-1-YL)BORATE LIGANDS [J].

JEFFERY, JC ;

STONE, FGA ;

WILLIAMS, GK .

POLYHEDRON, 1991, 10 (02) :215-219

[20] Synthesis, characterisation and reactivity of group six alkylidynes bearing the tridentate phosphine PPh(C2H4PPh2)2 'triphos'.: Crystal structure of mer-[W(NCMe)(CC6H4Me-4){PPh(C2H4PPh2)2}(CO)][BF4] [J].

Jeffery, JC ;

Weller, AS .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 548 (02) :195-203

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