Lewis酸诱导的阴离子侧端-端结合的二氮二铌氢化物配合物中的二氮裂解

Suzuki Naofumi, Ishida Yutaka, Kawaguchi Hiroyuki

Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8551, Japan.

Molecules. 2022 Aug 29;27(17):5553. doi: 10.3390/molecules27175553.

The side-on end-on dinitrogen hydride complex [{Na(dme)}{(O)Nb}(μ-η:η-N)(μ-H)] (, [O] = [(3,5-Bu-2-O-CH)CH]) was observed to undergo facile elimination of H and cleavage of the N-N bond in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN), AlMe, and ZnMe. Treatment of with 9-BBN and ZnMe afforded the nitride complex [{K(dme)}{(O)Nb}(μ-N)] (). The reaction of with AlMe afforded [{Na(dme)}{(O)AlMe}(NbMe)(μ-N)] (). The nitride complex was treated with 9-BBN and AlMe to form [{Na(dme)}{(O)Nb}(μ-NH)(μ-NBCH){Nb(OC)}] () and , respectively. Complex , , and were structurally characterized.

观察到侧端-端联氨配合物[{Na(dme)}{(O)Nb}(μ-η:η-N)(μ-H)]（，[O] = [(3,5-Bu-2-O-CH)CH]）在9-硼双环[3.3.1]壬烷（9-BBN）、AlMe和ZnMe存在下容易发生H消除和N-N键断裂。用9-BBN和ZnMe处理得到氮化物配合物[{K(dme)}{(O)Nb}(μ-N)]（）。用AlMe处理得到[{Na(dme)}{(O)AlMe}(NbMe)(μ-N)]（）。氮化物配合物用9-BBN和AlMe处理分别形成[{Na(dme)}{(O)Nb}(μ-NH)(μ-NBCH){Nb(OC)}]（）和。对配合物、和进行了结构表征。