Syntheses of Molybdenum Adamantylimido and t-Butylimido Alkylidene Chloride Complexes Using HCI and Diphenylnnethylphosphine

被引：13

作者：

Bukhryakov, Konstantin V. ^{[1
]}

VenkatRamani, Sudarsan ^{[1
]}

Tsay, Charlene ^{[1
]}

Hoveyda, Amir ^{[2
]}

Schrock, Richard R. ^{[1
]}

机构：

[1] MIT, Dept Chem 6 331, Cambridge, MA 02139 USA

[2] Boston Coll, Merkert Chem Ctr, Dept Chem, Chestnut Hill, MA 02467 USA

来源：

ORGANOMETALLICS | 2017年 / 36卷 / 21期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

OPENING METATHESIS POLYMERIZATION; RING-CLOSING METATHESIS; SELECTIVE CROSS-METATHESIS; ALT-B COPOLYMERS; 2,6-DIMESITYLPHENYLIMIDO LIGAND; TUNGSTEN ALKYLIDENE; OLEFIN METATHESIS; TERT-BUTYLIMIDO; CONTAIN; CATALYSTS;

D O I：

10.1021/acs.organomet.7b00647

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reactions between Mo(N-t-Bu)(2)(CH2-t-Bu)(2) or Mo(NAdamantyl)(2)(CH2CMe2Ph)(2) and 3 equiv of HCl in the presence of 1 equiv of PPh2Me yield Mo(NR)(CHR')(PPh2Me)Cl-2 complexes, from which Mo (NR)(CHR')(PPh2Me)(OAr)Clcomplexes (OAr = a 2,6-terphenoxide) can be prepared. The Mo(NR)(CHR')(PPh2Me)(OAr)Cl complexes were evaluated as cross-metathesis catalysts between cyclooctene and Z-1,2-dichloroethylene. The efficiencies of the test reaction for complexes in which OAr = OTPP, OHMT, OHIPT, or OHTBT (where OTPP is 2,3,5,6-tetraphenylphenoxide, OHMT is hexamethylterphenoxide, OHIPT is hexaisopropylterphenoxide, and OHTBT is hexa-t-butylterphenoxide) maximize when OAr is OHMT or OHIPT. Mo(N-t-Bu)(CH-t-Bu)(PPh2Me)Cl-2 is essentially inactive for the reaction between cyclooctene and Z-1,2-dichloroethylene. X-ray structural studies were carried out on Mo(NAd)(CHCMe2Ph)(PPh2Me)Cl-2, Mo(N-t-Bu)(CH-t-Bu)(PPh2Me)(OHMT)Cl, Mo(NAd)(CHCMe2Ph)(Cl)(OHTBT)(PMe3), and [Mo(NAd)(CHCMe2Ph)(PMe3)(Cl)](2)(mu-O), the product of the reaction between Mo(NAd)(CHCMe2Ph)(Cl)(OHTBT)(PMe3) and 0.5 equiv of water.

引用

页码：4208 / 4214

页数：7

共 48 条

[1] SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].