Nickel hydrides supported by a non-innocent diphosphine arene pincer: mechanistic studies of nickel-arene H-migration and partial arene hydrogenation.
نویسندگان
چکیده
Nickel hydrides supported by a terphenyl diphosphine were synthesized and found to undergo nickel-to-arene H-transfers. Some of the resulting complexes also undergo the reverse (C-to-Ni) H-migration, indicating the potential for storing H-equivalents in this type of pincer ligand. NMR spectroscopy, single crystal X-ray diffraction, and isotopic labeling studies investigating the mechanism of these processes are discussed.
منابع مشابه
Arene non-innocence in dinuclear complexes of Fe, Co, and Ni supported by a para-terphenyl diphosphine.
Cofacial Fe2, Co2, and Ni2 complexes supported by a para-terphenyl diphosphine ligand were prepared. Central arene deplanarization and a μ2:(η(3),η(3)) coordination mode suggest partial bisallyl character in the Fe2 and Co2 complexes. An oxidation induced shift in Fe2-arene binding highlights the non-innocent nature of the arene ligand.
متن کاملTrinuclear Nickel Complexes with Metal-Arene Interactions Supported by Tris- and Bis(phosphinoaryl)benzene Frameworks.
Triphosphine and diphosphine ligands with backbones designed to facilitate metal-arene interactions were employed to support multinuclear Ni complexes. Di- and trinuclear metal complexes supported by a triphosphine containing a triarylbenzene linker display diverse metal-arene binding modes. Multinuclear Ni halide complexes were isolated with strongly interacting metal centers bound to opposite...
متن کاملNickel-mediated hydrogenolysis of C-O bonds of aryl ethers: what is the source of the hydrogen?
Mechanistic studies of the hydrogenolysis of aryl ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni-arene interactions adjacent to the aryl-O bond was isolated. Heating led to aryl-O bond activation and generation of a nickel aryl methoxide complex. Formal β-H elimination from this species produced a nickel aryl hydride which can undergo reduct...
متن کاملSynthesis and C-C coupling reactivity of a dinuclear Ni(i)-Ni(i) complex supported by a terphenyl diphosphine.
Mono- and bimetallic complexes of nickel supported by a terphenyl diphosphine have been synthesized. The reported complexes show diverse metal-arene interactions in the solid state. Reactions of an o,o'-biphenyldiyl dinickel complex with CO and dichloroalkanes lead to fluorene derivatives, indicating the formation of carbon-carbon bonds at a bimetallic moiety.
متن کاملp-tert-Butyltetrathiatetramercaptocalix[4]arene as a sulfur-rich platform for molybdenum, tungsten and nickel.
p-tert-Butyltetrathiatetramercaptocalix[4]arene, [S(4)Calix(Bu(t))(SH)(4)], reacts with Mo(PMe(3))(6), W(PMe(3))(4)(eta(2)-CH(2)PMe(2))H and Ni(PMe(3))(4) to yield molybdenum, tungsten and nickel compounds in a sulfur-rich coordination environment.
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Journal of the American Chemical Society
دوره 133 11 شماره
صفحات -
تاریخ انتشار 2011