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
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.
引用
收藏
页码:2262 / 2266
页数:5
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共 34 条
[21]   SYNTHESIS OF AN ETA-2-CH(SME) CARBENE LIGAND BY PROTONATION OF THE CARBYNE IN [HB(PZ)3](CO)2W(=CSME) - A POSSIBLE MODEL STEP IN CO HYDROGENATION [J].
KIM, HP ;
KIM, S ;
JACOBSON, RA ;
ANGELICI, RJ .
ORGANOMETALLICS, 1984, 3 (07) :1124-1126
[22]   FORMATION OF 1,3-DIENE COMPLEXES UPON PROTONATION OF CYCLOPROPYLCARBYNE COMPLEXES [J].
KINGSBURY, KB ;
CARTER, JD ;
MCELWEEWHITE, L ;
OSTRANDER, RL ;
RHEINGOLD, AL .
ORGANOMETALLICS, 1994, 13 (05) :1635-1640
[23]   REGIOSELECTIVE AND STEREOSELECTIVE FORMATION OF CYCLOPENTENONES UPON PHOTOOXIDATION OF CYCLOPROPYL CARBYNE COMPLEXES [J].
KINGSBURY, KB ;
CARTER, JD ;
WILDE, A ;
PARK, H ;
TAKUSAGAWA, F ;
MCELWEEWHITE, L .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (22) :10056-10065
[24]   MOLECULAR-ORBITAL CALCULATIONS ON OCTAHEDRAL CARBYNE COMPLEXES - BONDING, STRUCTURE DEFORMATIONS, AND FRONTIER-CONTROLLED NUCLEOPHILIC ADDITIONS [J].
KOSTIC, NM ;
FENSKE, RF .
ORGANOMETALLICS, 1982, 1 (03) :489-496
[25]   MOLECULAR-ORBITAL CALCULATIONS ON CARBYNE COMPLEXES CPMN(CO)2CR+ AND (CO)5CRCNET2+ - FRONTIER-CONTROLLED NUCLEOPHILIC-ADDITION TO METAL-CARBON TRIPLE BOND [J].
KOSTIC, NM ;
FENSKE, RF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (16) :4677-4685
[26]   ACID-INDUCED CARBYNE-ACYL TRANSFORMATIONS [J].
KREISSL, FR ;
SIEBER, WJ ;
KELLER, H ;
RIEDE, J ;
WOLFGRUBER, M .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1987, 320 (01) :83-90
[27]   ACID-INDUCED CARBYNE-ACYL REARRANGEMENT - AN UNEXPECTED CC COUPLING REACTION [J].
KREISSL, FR ;
SIEBER, WJ ;
WOLFGRUBER, M ;
RIEDE, J .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1984, 23 (08) :640-640
[28]   REVERSIBLE ACYL-KETEN-UMWANDLUNG [J].
KREISSL, FR ;
KELLER, H ;
SCHUTT, W .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 441 (01) :75-80
[29]   Direct observation of a hydrogen abstraction product upon photooxidation of a tungsten cyclohexenyl carbyne complex [J].
Main, AD ;
McElweeWhite, L .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (19) :4551-4552
[30]   THE METAL-CARBON TRIPLE BOND IN CL(CO)4 CR=CH - A CAS SCF STUDY OF NEUTRAL CARBYNE COMPLEXES [J].
POBLET, JM ;
STRICH, A ;
WIEST, R ;
BENARD, M .
CHEMICAL PHYSICS LETTERS, 1986, 126 (02) :169-175