DIASTEREOMERIC SQUARE-PLANAR PLATINUM(II) AND PALLADIUM(II) COMPLEXES DUE TO RESTRICTED ROTATION ABOUT THE CHELATED M-N HETEROARYL BOND
DIASTEREOMERIC SQUARE-PLANAR PLATINUM(II) AND PALLADIUM(II) COMPLEXES DUE TO RESTRICTED ROTATION ABOUT THE CHELATED M-N HETEROARYL BOND
复制标题
由于螯合 M-N 杂芳基键旋转受限而形成非对映方平面铂 (II) 和钯 (II) 配合物
DOI：
10.1021/om00011a052
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发表时间：
1995
期刊：
影响因子：
2.8
通讯作者：
A. Arif
中科院分区：
文献类型：
--
作者：
P. Stang;B. Olenyuk;A. Arif
Pt; L=三乙基膦，V2 = 1，3-双（二苯基膦基）丙烷（dppp）或V2 =（CR）-（+）-2，2 ′-双（二苯基膦基）-1，1 ′-联萘（CR）-（-f）-BINAP））导致形成非对映体、正方形平面的阳离子络合物，其表现出围绕金属-氮杂芳基键的受限旋转。所有配合物均用常规的物理和光谱方法进行了表征，其中31 {} NMR谱是最有价值的。仅络合物[Pd（dppp）（异喹啉）2][OTf] 2（14）、[Pt（dppp）（异喹啉）2][OTi] 2（15）和[Pd-（（R）-（+）-BINAP）（异喹啉）2][OTf| 2（22）被发现是动态的，在室温下的NMR时间尺度。对这些化合物的31 {} NMR谱进行了变温研究。本文报道了[Pt（dppp）（quinoline）_2][OTf]_2（19）的X-射线晶体结构。[Pd（（我？）-（+）-BINAP）（异喹啉）2][OTf] 2（22）和[Pt（（R）-（+）-BINAP）（异喹啉）2][OTf] 2（23）在-20 ℃和室温下分别显示出三种不同的旋转异构体.讨论了手性双膦配体的不对称诱导作用对22和23的旋转异构体的立体异构比的影响。
Pt; L= triethylphosphine, V2 l, 3-bis (diphenylphosphino) propane (dppp) or V2 CR)-(+)-2, 2'-bis (diphenylphosphino)-l, l'-binaphthyl (CR)-(-f)-BINAP)) results in the formation of dias-tereomeric, square-planar, cationic complexes, which exhibit restricted rotation about the metal-nitrogen heteroaryl bond. All complexes were characterized by routine physical and spectroscopic methods, of which 31 {} NMR spectroscopy was most valuable. Only the complexes [Pd (dppp)(isoquinoline) 2][OTf] 2 (14),[Pt (dppp)(isoquinoline) 2][OTi] 2 (15), and [Pd-((R)-(+)-BINAP)(isoquinoline) 2][OTf| 2 (22) were found to be dynamic at ambient temperature on the NMR time scale. Variable-temperature studies of the 31 {} NMR spectra of these compounds were performed. The X-ray crystal structure of [Pt (dppp)(quinoline) 2][OTf] 2 (19) in one of its stereoisomeric (syn) forms is reported.[Pd ((i?)-(+)-BINAP)(isoquinoline) 2][OTf] 2 (22) and [Pt ((R)-(+)-BINAP)(isoquinoline) 2][OTf] 2 (23) exhibit three distinct rotamers at-20 C and ambient temperature, respectively. The role of asymmetric induction of the chiral bis-phosphine ligand on the stereoisomeric ratio of the rotamers of 22 and 23 is discussed.