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Mono- and dinuclear Ni(i) products formed upon bromide abstraction from the Ni(i) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br]†
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-12-05 00:00:00 , DOI: 10.1039/c7dt04187j
William J. M. Blackaby 1, 2, 3, 4 , Sara Sabater 1, 2, 3, 4 , Rebecca C. Poulten 1, 2, 3, 4 , Michael J. Page 1, 2, 3, 4 , Andrea Folli 4, 5, 6, 7 , Vera Krewald 1, 2, 3, 4 , Mary F. Mahon 1, 2, 3, 4 , Damien M. Murphy 4, 5, 6, 7 , Emma Richards 4, 5, 6, 7 , Michael K. Whittlesey 1, 2, 3, 4
Affiliation  

Bromide abstraction from the three-coordinate Ni(I) ring-expanded N-heterocyclic carbene complex [Ni(6-Mes)(PPh3)Br] (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) with TlPF6 in THF yields the T-shaped cationic solvent complex, [Ni(6-Mes)(PPh3)(THF)][PF6] (2), whereas treatment with NaBArF4 in Et2O affords the dimeric Ni(I) product, [{Ni(6-Mes)(PPh3)}2(μ-Br)][BArF4] (3). Both 2 and 3 act as latent sources of the cation [Ni(6-Mes)(PPh3)]+, which can be trapped by CO to give [Ni(6-Mes)(PPh3)(CO)]+ (5). Addition of [(Et3Si)2(μ-H)][B(C6F5)4] to 1 followed by work up in toluene results in the elimination of phosphine as well as halide to afford a co-crystallised mixture of [Ni(6-Mes)(η2-C6H5Me)][B(C6F5)4] (4), and [6MesH⋯C6H5Me][B(C6F5)4]. Treatment of 1 with sodium salts of more strongly coordinating anions leads to substitution products. Thus, NaBH4 yields the neutral, diamagnetic dimer [{Ni(6-Mes)}2(BH4)2] (6), whereas NaBH3(CN) gives the paramagnetic monomeric cyanotrihydroborate complex [Ni(6-Mes)(PPh3)(NCBH3)] (7). Treatment of 1 with NaOtBu/NHPh2 affords the three-coordinate Ni(I) amido species, [Ni(6-Mes)(PPh3)(NPh2)] (8). The electronic structures of 2, 5, 7 and 8 have been analysed in comparison to that of previously reported 1 using a combination of EPR spectroscopy and density functional theory.

中文翻译:

从Ni(i)扩环的NHC络合物[Ni(6-Mes)(PPh 3)Br]中提取溴化物而形成的单 核和双核Ni(i)产物

从三坐标Ni(I)环扩展的N-杂环卡宾络合物[Ni(6-Mes)(PPh 3)Br](1 ; 6-Mes = 1,3-bis(2,4,6 )提取溴化物-三甲基苯基)-3,4,5,6-四氢嘧啶-2-亚基)与TlPF 6在THF中的反应生成T形阳离子溶剂络合物[Ni(6-Mes)(PPh 3)(THF)] [PF 6 ](2),而在Et 2 O中用NaBAr F 4处理得到二聚Ni(I)产物[{Ni(6-Mes)(PPh 3)} 2(μ-Br)] [BAr F 4 ](3)。双方23充当阳离子[Ni(6-Mes)(PPh 3)] +的潜在来源,可以被CO捕集而得到[Ni(6-Mes)(PPh 3)(CO)] +5)。将[(Et 3 Si)2(μ-H)] [B(C 6 F 54 ]添加至1,然后在甲苯中进行后处理可消除膦和卤化物,从而制得共结晶混合物的[镍(6-MES)(η 2 -C 6 ħ 5 Me)中] [B(C 6 ˚F 54 ](4),和[6MesH⋯ç 6H 5 Me] [B(C 6 F 54 ]。用具有更强配位阴离子的钠盐处理1会产生取代产物。因此,NaBH 4产生中性,反磁性的二聚体[{Ni(6-Mes)} 2(BH 42 ](6),而NaBH 3(CN)则提供顺磁性单体氰基三氢硼酸酯络合物[Ni(6-Mes)( PPh 3)(NCBH 3)](7)。用NaO t Bu / NHPh 2处理1得到三坐标的Ni(I)酰胺类,[Ni(6-Mes)(PPh 3)(NPh 2)](8)。的电子结构2578已经相较于先前进行了分析报道1使用EPR光谱和密度泛函理论的组合。
更新日期:2017-12-05
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