Kristallstruktur von [ZnH(NPMe3)]4, einem tetrameren Phosphaniminato-Komplex des Zinks mit terminalen Hydrido-Liganden

Abstract

Crystal Structure of [ZnH(NPMe3)]4, a Tetrameric Phosphoraneiminato Complex of Zinc with Terminal Hydrido Ligands The crystal structure of the title compound, which crystallizes as [ZnH(NPMe3)]4 · 4 THF forming colourless, very reactive blocks, obtained by recrystallization from toluene, reveals discrete tetrameric molecules with heterocubane structure with almost undistorted Zn4N4 cubic skeletons. The hydrido ligands assume terminal exocyclic positions with Zn–H bond lengths of 150 pm in average.

Molecular Main Group Metal Hydrides

“… a 2 equiv of HBpin. b Cyclohexanone. c 2-Methylcyclohexanone. d 2-Cyclohexen-1-one. e Adamantanone. Data taken from ref . f Entries labelled with “A” arise from Ge-mediated catalysis, while those marked as “B” result from Sn-promoted catalysis. …”

“…Amido-supported zinc hydrides made an early entry into the open literature with the structurally authenticated dimer [(Me 2 NCH 2 CH 2 NMe)­Zn­(μ-H)] 2 ( 381 ) and cubane [HZn­(μ 3 -NPMe 3 )] 4 ( 382 ) serving as representative examples prior to 2001. More recently, Hevia and coworkers obtained the carbene-bound amidozinc hydride adducts [IPr·ZnH­{N­(SiMe 3 ) 2 }] ( 383 ) and [IPr·{Zn­(μ-H) 2 } 2 {Zn­(μ-H)­N­(SiMe 3 ) 2 } 2 ·IPr] ( 384 ) from the reaction of in situ generated IPr·Zn­{N­(SiMe 3 ) 2 } 2 ( 385 ) with the hydride sources PhSiH 3 and Me 2 NH·BH 3 , respectively (Scheme ).…”

“…703,704 Related borohydride complexes have also been generated by the addition of 9-BBN to β-diketiminate-bound aluminum hydrides. 705 ( Mes Nacnac)AlH 2 (486) was also found to readily reduce an equivalent of CO 2 (per Al center), forming the formate-bridged aluminum hydride dimer [{( Mes Nacnac)Al(μ-H)(μ-OC(H)O)] 2 (498). 706 Structurally related ketiminate supported aluminum hydrides are known to yield aluminum formate species.…”

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO2

“…1a,18 These complexes exhibit a range of structures, including clusters, 15 cubanes, 6,11,13 dimers, 1c,12a,14,17,19 and mononuclear structures. 2b,9b,12d,16,18 The carbon dioxide insertion chemistry of only a few of these hydride complexes has been studied.…”

“…Various zinc hydride complexes, of the formulation LZnH, have been reported where L, a monoanionic ancillary ligand, is selected from amino/pyridyl amides, 1c , 8 tris(pyrazoyl)hydroborates, 2 , 9 3,5-disubstituted pyrazoles, 10 phosphorane iminates, 11 β-diketiminates, 12 alkoxides, 6 , 13 2,6-dialkylphenyls, 14 pyridyl-substituted tris(trimethylsilyl)methanides, 15 tris(4,4-dimethyl-2-oxazolinyl)phenylborate, 1b , 16 acetimidinato, 17 and tris(2-pyridylthio)methyl. 1a , 18 These complexes exhibit a range of structures, including clusters, 15 cubanes, 6 , 11 , 13 dimers, 1c , 12a , 14 , 17 , 19 and mononuclear structures. 2b , 9b , 12d , 16 , 18 The carbon dioxide insertion chemistry of only a few of these hydride complexes has been studied.…”