Rh(II) and Rh(I) two-legged piano-stool complexes: structure, reactivity, and electronic properties.
Rh(II) and Rh(I) two-legged piano-stool complexes: structure, reactivity, and electronic properties.
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Rh(II) 和 Rh(I) 双腿琴凳复合物：结构、反应性和电子特性。
DOI：
10.1021/ic0204981
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发表时间：
2003
期刊：
影响因子：
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通讯作者：
Rheingold,ArnoldL
中科院分区：
文献类型：
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作者：
Dixon,FeliciaM;Masar3rd,MartinS;Doan,PeterE;Farrell,JoshuaR;ArnoldJr,FrederickP;Mirkin,ChadA;Incarvito,ChristopherD;Zakharov,LevN;Rheingold,ArnoldL
以1，4-双[4-（二苯基膦基）丁基]-2，3，5，6-四甲基苯为配体，合成了一种具有两条腿的钢琴凳构型的单核Rh（II）配合物[（η1：η6：η1- 1，4-双[4-（二苯基膦基）丁基]-2，3，5，6-四甲基苯）Rh][PF 6] 2，6+。报道了这种新型配合物的结构和电子性质，包括单晶EPR分析。该络合物可以与其Rh（I）形式干净地相互转化，从而可以比较两种氧化态的结构性质和反应性。Rh（I）form 6与CO、叔丁基异氰化物和乙腈反应，形成一系列15元单核环番[（η1：η1- 1，4-双[4-（二苯基膦基）丁基]-2，3，5，6-四甲基苯）Rh（CO）3][PF 6]（8）、[（η1：η1- 1，4-双[4-（二苯基膦基）丁基]-2，3，5，6-四甲基苯）Rh（CNC（CH 3）3）2][PF 6]（10）和[（η1：η1- 1，4-双[4-（二苯基膦基）丁基]-2，3，5，6-四甲基苯）Rh（CO）（CH 3CN）][PF 6]（11）。Rh（II）络合物6+与相同的小分子反应，但在较短的时间内，形成相同的Rh（I）产物。此外，还合成了一个两足钢琴粪便模型配合物[（η1：η6：η1- 1，4-bis[3-（diphenylphosphino）propoxy]-2，3，5，6-tetramethylbenzene）Rh][B（C6 F5）4]，5，并进行了表征，以供比较。报道了配合物5、6、6+和11的固态结构。5的结构数据：三斜晶系; P1 β; a= 10.1587（7）°;B= 11.5228（8）°;c= 17.2381（12）°; α = 96.4379（13）°; β = 91.1870（12）°; γ = 106.1470（13）°;Z= 2.6：三斜晶系;P1 °;a=11.1934（5）°;B=12.4807（6）°;c= 16.1771（7）°; α = 81.935（7）°; β = 89.943（1）°; γ = 78.292（1）°;Z= 2.6+：单斜晶系;P2（1）/n;a= 11.9371（18）;B= 32.401（5）;c= 12.782（2）; β = 102.890（3）°;Z= 4.11：三斜晶系;P1;a= 13.5476（7）; B= 13.8306（7）°;c= 14.9948（8）°; α = 74.551（1）°; β = 73.895（1）°; γ = 66.046（1）°;Z= 2。
The ligand 1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene,3, was used to synthesize a mononuclear Rh(II) complex [(η1:η6:η1-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh][PF6]2,6+, in a two-legged piano-stool geometry. The structural and electronic properties of this novel complex including a single-crystal EPR analysis are reported. The complex can be cleanly interconverted with its Rh(I) form, allowing for a comparison of the structural properties and reactivity of both oxidation states. The Rh(I) form6reacts with CO,tert-butyl isocyanide, and acetonitrile to form a series of 15-membered mononuclear cyclophanes [(η1:η1-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)3][PF6] (8), [(η1:η1-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CNC(CH3)3)2][PF6] (10), and [(η1:η1-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(CH3CN)][PF6] (11). The Rh(II) complex6+reacts with the same small molecules, but over shorter periods of time, to form the same Rh(I) products. In addition, a model two-legged piano-stool complex [(η1:η6:η1-1,4-bis[3-(diphenylphosphino)propoxy]-2,3,5,6-tetramethylbenzene)Rh][B(C6F5)4],5, has been synthesized and characterized for comparison purposes. The solid-state structures of complexes5,6,6+, and11are reported. Structure data for5: triclinic;P1̄;a= 10.1587(7) Å;b= 11.5228(8) Å;c= 17.2381(12) Å; α = 96.4379(13)°; β = 91.1870(12)°; γ = 106.1470(13)°;Z= 2.6: triclinic;P1̄;a=11.1934(5) Å;b=12.4807(6) Å;c= 16.1771(7) Å; α = 81.935(7)°; β = 89.943(1)°; γ = 78.292(1)°;Z= 2.6+: monoclinic;P2(1)/n;a= 11.9371(18) Å;b= 32.401(5) Å;c= 12.782(2) Å; β = 102.890(3)°;Z= 4.11: triclinic;P1̄;a= 13.5476(7) Å;b= 13.8306(7) Å;c= 14.9948(8) Å; α = 74.551(1)°; β = 73.895(1)°; γ = 66.046(1)°;Z= 2.