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由具有强双（膦基）-1,8-萘啶配体的二铜μ-硼基配合物介导的CO和CS的乙硼烷还原反应

Diborane Reductions of CO and CS Mediated by Dicopper μ-Boryl Complexes of a Robust Bis(phosphino)-1,8-naphthyridine Ligand.

作者信息

See Matthew S, Ríos Pablo, Tilley T Don

机构信息

Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.

Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.

出版信息

Organometallics. 2024 May 3;43(10):1180-1189. doi: 10.1021/acs.organomet.4c00122. eCollection 2024 May 27.

DOI:10.1021/acs.organomet.4c00122
PMID:38817536
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11134609/
Abstract

A dinucleating 1,8-naphthyridine ligand featuring fluorene-9,9-diyl-linked phosphino side arms (PNNP) was synthesized and used to obtain the cationic dicopper complexes , [(PNNP)Cu(μ-Ph)][NTf]; [NTf] = bis(trifluoromethane)sulfonimide, , [(PNNP)Cu(μ-CCPh)][NTf], and , [(PNNP)Cu(μ-OBu)][NTf]. Complex reacted with diboranes to afford dicopper μ-boryl species (, with μ-Bcat; cat = catecholate and , with μ-Bpin; pin = pinacolate) that are more reactive in C(sp)-H bond activations and toward activations of CO and CS, compared to dicopper μ-boryl complexes supported by a 1,8-naphthyridine-based ligand with di(pyridyl) side arms. The solid-state structures and DFT analysis indicate that the higher reactivities of and relate to changes in the coordination sphere of copper, rather than to perturbations on the Cu-B bonding interactions. Addition of xylyl isocyanide (CNXyl) to gave , [(PNNP)Cu(μ-Bcat)(CNXyl)][NTf], demonstrating that the lower coordination number at copper is chemically significant. Reactions of and with CO yielded the corresponding dicopper borate complexes (, [(PNNP)Cu(μ-OBcat)][NTf]; , [(PNNP)Cu(μ-OBpin)][NTf]), with demonstrating catalytic reduction in the presence of excess diborane. Related reactions of and with CS provided insertion products , {[(PNNP)Cu][μ-SC(Bcat)]}[NTf], and , [(PNNP)Cu(μ,κ-SCBpin)][NTf], respectively. These products feature Cu-S-C-B linkages analogous to those of proposed CO insertion intermediate.

摘要

合成了一种具有芴-9,9-二基连接膦侧臂（PNNP）的双核1,8-萘啶配体，并用于制备阳离子二铜配合物，即[(PNNP)Cu(μ-Ph)][NTf]；[NTf] = 双（三氟甲烷）磺酰亚胺，[(PNNP)Cu(μ-CCPh)][NTf]，以及[(PNNP)Cu(μ-OBu)][NTf]。配合物 与二硼烷反应生成二铜μ-硼基物种（，μ-Bcat；cat = 儿茶酚盐，以及，μ-Bpin；pin = 频哪醇盐），与由具有二（吡啶基）侧臂的基于1,8-萘啶的配体支撑的二铜μ-硼基配合物相比，这些物种在C(sp)-H键活化以及对CO和CS的活化方面更具反应性。固态结构和DFT分析表明，和 的较高反应性与铜配位球的变化有关，而不是与Cu-B键相互作用的扰动有关。向 中加入二甲苯基异腈（CNXyl）得到[(PNNP)Cu(μ-Bcat)(CNXyl)][NTf]，表明铜的较低配位数具有化学意义。和 与CO反应生成相应的二铜硼酸盐配合物（，[(PNNP)Cu(μ-OBcat)][NTf]；，[(PNNP)Cu(μ-OBpin)][NTf]），其中 在过量二硼烷存在下表现出催化还原作用。和 与CS的相关反应分别提供了插入产物{[(PNNP)Cu][μ-SC(Bcat)]}[NTf]和[(PNNP)Cu(μ,κ-SCBpin)][NTf]。这些产物具有与所提出的CO插入中间体类似的Cu-S-C-B键。

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