Wooten Alfred, Carroll Patrick J, Maestri Aaron G, Walsh Patrick J
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
J Am Chem Soc. 2006 Apr 12;128(14):4624-31. doi: 10.1021/ja058700x.
This report describes the solid-state structures of a series of divinylzinc complexes, one of which represents the only structurally characterized zinc(II) pi-complex. Vinylzinc reagents, Zn[C(Me)=CH2]2 (1) and Zn[C(H)=CMe2]2 (2), have been synthesized and isolated as white crystalline solids in 66 and 72% yield, respectively. Each compound exhibits an infinite polymeric architecture in the solid state via a series of zinc-pi (1) and zinc-sigma-bonded (2) bridging interactions. Addition of chelating ligands to these divinylzinc compounds allowed isolation of the monomeric adducts (bipy)Zn[C(Me)=CH2]2 (1.bipy), (tmeda)Zn[C(Me)=CH2]2 (1tmeda), (bipy)Zn[C(H)=CMe2]2 (2bipy), and (tmeda)Zn[C(H)=CMe2]2 (2tmeda), of which 1bipy, 2bipy, and 2tmeda have been characterized crystallographically.
本报告描述了一系列二乙烯基锌配合物的固态结构,其中之一是唯一具有结构表征的锌(II)π配合物。乙烯基锌试剂Zn[C(Me)=CH₂]₂(1)和Zn[C(H)=CMe₂]₂(2)已被合成并分离为白色结晶固体,产率分别为66%和72%。每种化合物在固态中通过一系列锌-π(1)和锌-σ键合(2)桥连相互作用呈现出无限聚合物结构。向这些二乙烯基锌化合物中加入螯合配体,可分离出单体加合物(bipy)Zn[C(Me)=CH₂]₂(1·bipy)、(tmeda)Zn[C(Me)=CH₂]₂(1·tmeda)、(bipy)Zn[C(H)=CMe₂]₂(2·bipy)和(tmeda)Zn[C(H)=CMe₂]₂(2·tmeda),其中1·bipy、2·bipy和2·tmeda已通过晶体学表征。