PSnP钳型亚锡Sn(NCH 2 P t Bu 2)2 C 6 H 4的合成及一些配位化学,试图制备PSiP类似物,以及E原子对E(NCH 2)分子结构的影响P t Bu 2)2 C 6 H 4(E = C,Si,Ge,Sn)†
摘要:
通过用Li 2(NCH 2 P t Bu 2)2 C 6 H处理SnCl 2来制备非供体稳定的PSnP夹钳型亚锡Sn(NCH 2 P t Bu 2)2 C 6 H 4(1)。4。通过还原(以前未知的)硅烷SiCl 2(NCH 2 P t Bu 2)2 C 6 H 4(以前未知)来合成类似的PSiP甲硅烷基的所有尝试。2),SiHCl(NCH 2 P t Bu 2)2 C 6 H 4(3)和SiH(HMDS)(NCH 2 P t Bu 2)2 C 6 H 4(4 ; HMDS = N(SiMe 3)2)一直没有成功。借助DFT计算已经合理化了亚锡1(通过X射线晶体学测定)的几乎平面的分子结构(不包括叔丁基),这表明在二膦三烯E(NCH)系列中2 P t Bu 2) 2 C 6 H 4(E = C,Si,Ge,Sn),具有E = Ge和Sn的最稳定构型的两个P原子都非常接近EN 2 C 6 H
From a PGeP Pincer-Type Germylene to Metal Complexes Featuring Chelating (Ir) and Tripodal (Ir) PGeP Germyl and Bridging (Mn<sub>2</sub>) and Chelating (Ru) PGeP Germylene Ligands
作者:Javier Brugos、Javier A. Cabeza、Pablo García-Álvarez、Enrique Pérez-Carreño
DOI:10.1021/acs.organomet.8b00171
日期:2018.5.14
coordination modes of a PGeP chloridogermyl ligand (Ge,P-chelating and P,Ge,P-tripodal) and a PGeP germyleneligand (P,Ge,P-bridging and Ge,P-chelating) have been identified in coordination compounds resulting from reactions of the PGeP pincer-type diphosphane-germylene Ge(NCH2PtBu2)2C6H4 (1) with iridium(I), manganese(0), and ruthenium(II) complex reagents. Germylene 1 reacted with [Ir2(μ-Cl)2(η4-cod)2]
在配位化合物中,已鉴定出PGeP氯锗甲基配体(Ge,P-螯合和P,Ge,P-三脚架)和PGeP ylene烯配体(P,Ge,P-桥接和Ge,P-螯合)的不同配位模式。由PGeP夹钳型二膦-锗烷Ge(NCH 2 P t Bu 2)2 C 6 H 4(1)与铱(I),锰(0)和钌(II)络合剂反应制得。异戊二烯1用的[Ir反应2(μ-Cl)的2(η 4 -cod)2 ](COD = 1,5-环辛二烯),得到的[Ir κ 2的Ge,P -GeCl(NCH 2 P吨卜2)2 C ^ 6 ħ 4 }(η 4 -cod)](2),其中包含一个锗,P-螯合PGeP chloridogermyl配体和不协调的膦基团与锗原子弱相互作用。一氧化碳容易移位的鳕鱼配体2,得到的二羰基衍生物的[Ir κ 3 P,Ge,P -GeCl(NCH 2 P t Bu 2)2 C 6 H 4 }(CO)2 ](3),其中
Synthesis and initial transition metal chemistry of the first PGeP pincer-type germylene
作者:Lucía Álvarez-Rodríguez、Javier Brugos、Javier A. Cabeza、Pablo García-Álvarez、Enrique Pérez-Carreño、Diego Polo
DOI:10.1039/c6cc09283g
日期:——
The first PGeP pincer-type germylene has been synthesized. Its divalent Ge atom easily inserts into M–M and M–Cl bonds, giving rise to products that contain a PGeP bridging germylene or a PGeP pincer chlorogermyl ligand.
Syntheses of PBP Pincer Iridium Complexes: A Supporting Boryl Ligand
作者:Yasutomo Segawa、Makoto Yamashita、Kyoko Nozaki
DOI:10.1021/ja9037092
日期:2009.7.8
and demonstrated its complexation with iridium(I) to afford the coordinativelyunsaturated [PBP](hydrido)chloroiridium complex 3 via B-H oxidative addition. The reaction of 3 with carbon monoxide produced [PBP](hydrido)chloro(carbonyl)iridium 7. The longer Ir-Cl bond length of 7 than that of 8 revealed a stronger sigma-donor ability of the PBP ligand than that of PCP. Complex 3 was also converted to
Boryl‐Based Pincer Systems: New Avenues in Boron Chemistry
作者:Jarl Ivar van der Vlugt
DOI:10.1002/anie.200904795
日期:2010.1.8
B? Incorporation of BH into tridentate ligands has recently allowed the isolation of the first boryl‐basedpincer complexes. Functionalized diaminoborane and m‐carbaborane (see picture) form Ir and Pd complexes, respectively. Novel reactivity, including in catalysis, is expected to result from the Mboryl bond and electronic communication with the specific ligand framework.
Formation of Chlorosilyl Pincer-Type Rhodium Complexes by Multiple Si–H Activations of Bis(phosphine)/Dihydrosilyl Ligands
作者:Matthew T. Whited、Alexander M. Deetz、Joseph W. Boerma、Daniel E. DeRosha、Daron E. Janzen
DOI:10.1021/om5006319
日期:2014.10.13
bis(phosphine)/dihydrosilyl ligands at rhodium(I) sources is reported. Irrespective of the substitution at silicon (diaryl versus diamino), multiple Si–H activations and chloride migration afford tridentate bis(phosphine)/chlorosilyl complexes of Rh(I). For the diarylsilyl ligand, reaction with a cationic rhodium(I) triflate precursor gives the analogous triflatosilyl complex. The [P2Si]H2 proligands
报道了在铑(I)源上两个双(膦)/二氢甲硅烷基配体的合成和金属化。不论在硅上的取代(二芳基对二氨基),多次Si–H活化和氯离子迁移都能得到Rh(I)的三齿双(膦)/氯甲硅烷基络合物。对于二芳基甲硅烷基配体,与阳离子三氟甲磺酸铑(I)前体反应得到类似的三氟甲硅烷基络合物。[P 2 Si] H 2配体及其Rh配合物为探索金属/硅的协同反应性提供了独特的机会。