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首页> 外文期刊>Chemistry: A European journal >Binding H-2, N-2, H-, and BH3 to transition-metal sulfur sites: Synthesis and properties of [Ru(L)(PR3)(N2Me2S2)] complexes (L = eta(2)-H-2, H-, BH3; R = Cy, iPr)
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Binding H-2, N-2, H-, and BH3 to transition-metal sulfur sites: Synthesis and properties of [Ru(L)(PR3)(N2Me2S2)] complexes (L = eta(2)-H-2, H-, BH3; R = Cy, iPr)

机译：将H-2，N-2，H-和BH3结合到过渡金属硫位点：[Ru（L）（PR3）（N2Me2S2）]络合物的合成和性质（L = eta（2）-H-2， H-，BH3; R = Cy，iPr）

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摘要

The reactions of [Ru(N-2)-(PR3)(`N2Me2S2')] [`N2Me2S2'=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2- benzenethiolate)(2-)] [la (R=iPr), 1b (R=Cy)] and [mu-N-2{Ru(N-2)(PiPr(3))(`N2Me2S2')}(2)] (1c) with H-2, NaBH4, and NBu4BH4, intended to reduce the N-2 ligands, led to substitution of N-2 and formation of the new complexes [Ru(H-2)(PR3)(`N2Me2S2')] [2a (R=iPr), 2b (R=Cy)], [Ru(BH3)(PR3)(`N2Me2S2')] [3a (R= iPr), 3b (R=Cy)], and [Ru(H)(PR3)(`N2Me2S2')](-) [4a (R= iPr), 4b (R=Cy)]. The BH3 and hydride complexes 3a, 3b, 4a, and 4b were obtained subsequently by rational synthesis from la or 1b and BH3.THF or LiBEt3H. The primary step in all reactions probably is the dissociation of N-2 from the N-2 complexes to give coordinatively unsaturated [Ru(PR3)(`N2Me2S2')] fragments that add H-2, BH4-, BH3, or H-. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H-2)(PR3)(`N2Me2S2')] [2a (R=iPr), 2b (R=Cy)], [Ru(BH3)(PiPr(3))(`N2Me2S2')] (3 a), [Li(THF)(2)] [Ru(H)(PiPr(3)) (`N2Me2S2')] ([Li(THF)(2)]-4a), and NBu4[Ru(H)(PCy3)(`N2Me2S2')] (NBu4-4b) were determined by X-ray crystal structure analysis. Measurements of the NMR relaxation time T-1 corroborated the H-2 bonding mode of the H-2 ligands in 2 a (T-1=35 ms) and 2b (T-1=21 ms). The H,D coupling constants of the analogous HD complexes HD-2a ((1)J(H,D) = 26.0 Hz) and HD-2b ((1)J(H,D)= 25.9 Hz) enabled calculation of the HD distances, which agreed with the values found by X-ray crystal structure analysis (2 a: 92 pm (X-ray) versus 98 pm (calculated), 2b: 99 versus 98 pm). The BH3 entities in 3a and 3b bind to one thiolate donor of the [Ru(PR3)(`N2Me2S2')] fragment and through a B-H-Ru bond to the Ru center. The hydride complex anions 4a and 4b are extremely Bronsted basic and are instantanously protonated to give the eta(2)-H-2 complexes 2a and 2b.
机译：[Ru（N-2）-（PR3）（'N2Me2S2'）] ['N2Me2S2'= 1,2-乙二胺-N，N'-二甲基-N，N'-双（2-苯硫醇酯）的反应（2-）] [la（R = iPr），1b（R = Cy）]和[mu-N-2 {Ru（N-2）（PiPr（3））（'N2Me2S2'）}（2）] （1c）用H-2，NaBH4和NBu4BH4还原N-2配体，导致N-2取代并形成新的络合物[Ru（H-2）（PR3）（'N2Me2S2'） ] [2a（R = iPr），2b（R = Cy）]，[Ru（BH3）（PR3）（'N2Me2S2'）] [3a（R = iPr），3b（R = Cy）]和[Ru （H）（PR 3）（'N 2 Me 2 S 2'）]（-）[4a（R ＝ iPr），4b（R ＝ Cy）]。随后通过1a或1b和BH3.THF或LiBEt3H的合理合成获得BH3和氢化物配合物3a，3b，4a和4b。所有反应的第一步可能是将N-2从N-2络合物中解离，以产生配位不饱和的[Ru（PR3）（'N2Me2S2'）]片段，其中添加H-2，BH4-，BH3或H- 。所有配合物均通过元素分析和常用光谱法进行了全面表征。 [Ru（H-2）（PR3）（`N2Me2S2'）] [2a（R = iPr），2b（R = Cy）]，[Ru（BH3）（PiPr（3））（`N2Me2S2 '）]（3 a），[Li（THF）（2）] [Ru（H）（PiPr（3））（'N2Me2S2'）]（[Li（THF）（2）]-4a）和NBu4通过X射线晶体结构分析确定[Ru（H）（PCy3）（'N2Me2S2'）]（NBu4-4b）。 NMR弛豫时间T-1的测量证实了在2a（T-1 = 35ms）和2b（T-1 = 21ms）中H-2配体的H-2键合模式。类似HD复合物HD-2a（（1）J（H，D）= 26.0 Hz）和HD-2b（（1）J（H，D）= 25.9 Hz）的H，D耦合常数使得HD距离，与通过X射线晶体结构分析得出的值一致（2 a：92 pm（X射线）对98 pm（计算得出），2b：99对98 pm）。 3a和3b中的BH3实体与[Ru（PR3）（'N2Me2S2'）]片段的一个硫醇盐供体结合，并通过B-H-Ru键与Ru中心键合。氢化物络合物阴离子4a和4b具有极强的布朗斯台德碱性，并瞬间质子化，得到eta（2）-H-2络合物2a和2b。

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