The Question of cis versus trans Configuration in Octahedral Metal Diketonates: An In-Depth Investigation on Diorganobis(4-acyl-5-pyrazolonato)tin(IV) Complexes
The Question of cis versus trans Configuration in Octahedral Metal Diketonates: An In-Depth Investigation on Diorganobis(4-acyl-5-pyrazolonato)tin(IV) Complexes
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八面体金属二酮中的顺式与反式构型问题：二有机双(4-酰基-5-吡唑啉酮)锡(IV)配合物的深入研究
DOI：
10.1002/ejic.201101050
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发表时间：
2012
影响因子：
2.3
通讯作者：
Caruso F
中科院分区：
文献类型：
--
作者：
Caruso F
4-酰基-5-吡唑啉酮的二有机锡（IV）衍生物Q2 SnR 2 [HQ = 3-甲基-1-苯基-4-R-5-吡唑啉酮：HQnPe，R =新戊基羰基; HQiPr，R =异丙基羰基; HQtBu，R =叔丁基羰基; HQCy，R =环己基羰基; HQCp，R =环戊基羰基; HQEtCp，R =（乙基环戊基）羰基]的合成和光谱（IR、远IR、1H、13 C和119 Sn NMR）和结构（X射线）表征。HQtBu的酰基片段中的空间体积在（QtBu）2SnMe 2的溶液中诱导部分解离，所述（QtBu）2SnMe 2作为六配位和五配位锡物种的平衡混合物存在。给出了几种代表性配合物的单晶X射线结构测定。虽然二烷基锡（IV）配合物总是反式-八面体，但二苯基锡（IV）衍生物以固态存在，其具有两个呈反式排列的苯基基团。DMol 3和CASTEP DFT研究这一前所未有的顺式，和相应的transformations，显示前者是稍微更稳定，与衍射研究。固态119 Sn交叉极化魔角旋转NMR光谱数据表明，表征二苯基（IV）衍生物的各向同性化学位移（δiso，mas）和化学位移各向异性/跨距（Δδ/Ω）明显从相应的二甲基和二正丁基衍生物的测量值中去除，从而进一步证明了二苯基（IV）系统中的稳定构型。这一点得到了GIPAW DFT计算的支持，GIPAW DFT计算使用CASTEP代码对完全弛豫结构的119 Sn各向同性位移和化学位移各向异性/跨度进行了计算，该代码提供了顺式二苯基（IV）排列与119 Sn NMR光谱参数中报告的差异之间的直接联系。
Diorganotin(IV) derivatives of 4‐acyl‐5‐pyrazolones Q2SnR2[HQ = 3‐methyl‐1‐phenyl‐4‐R‐5‐pyrazolone: HQnPe, R = neopentylcarbonyl; HQiPr, R = isopropylcarbonyl; HQtBu, R =tert‐butylcarbonyl; HQCy, R = cyclohexylcarbonyl; HQCp, R = cyclopentylcarbonyl; HQEtCp, R = (ethylcyclopentyl)carbonyl] have been synthesized and characterized spectroscopically (IR, far‐IR,1H,13C and119Sn NMR) and structurally (X‐ray). Steric bulkiness in the acyl fragment of HQtBuinduces partial dissociation in solution of (QtBu)2SnMe2, which exists as an equilibrium mixture of six‐ and five‐coordinate tin species. Single‐crystal X‐ray structure determinations of several representative complexes are presented. Whereas the dialkyltin(IV) complexes are alwaystrans‐octahedral, a diphenyltin(IV) derivative exists in the solid state that has the two phenyl groups in acisarrangement. DMol3 and CASTEP DFT studies of this unprecedentedcis, and the correspondingtransconfigurations, show the former to be slightly more stable, in agreement with the diffraction study. Solid‐state119Sn cross‐polarization magic‐angle spinning NMR spectroscopic data show that the isotropic chemical shifts (δiso,mas) and chemical‐shift anisotropies/spans (Δδ/Ω) that characterize the diphenyl(IV) derivatives are markedly removed from values measured for the corresponding dimethyl and di‐n‐butyl derivatives, thereby adding further evidence for a stablecisconfiguration in the diphenyl(IV) systems. This is supported by GIPAW DFT calculation of the119Sn isotropic shifts and chemical‐shift anisotropies/spans from fully relaxed structures by using the CASTEP code, which provides a direct link between thecisdiphenyl(IV) arrangement and the reported differences in the119Sn NMR spectroscopic parameters.
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119Sn-NMR参数
影响因子：
--
作者：
Bernd Wrackmeyer
通讯作者：
Bernd Wrackmeyer
阴离子 4-酰基-5-吡唑啉酮配体的锡 (IV) 和有机锡 (IV) 衍生物：合成、光谱表征（IR、远红外、119Sn mössbauer、1H、13C 和 119Sn NMR）以及溶液晶体和分子结构中的行为反式二苯基双[1-苯基-3-甲基-4-(4-溴苯甲酰基)-吡唑啉
影响因子：
2.3
作者：
F. Caruso;D. Leonesi;F. Marchetti;E. Rivarola;M. Rossi;V. Tomov;C. Pettinari
通讯作者：
C. Pettinari
双(4-酰基吡唑啉-5-ate)二有机锡物种的不寻常构型
影响因子：
2.8
作者：
F. Caruso;M. Rossi;F. Marchetti;C. Pettinari
通讯作者：
C. Pettinari
二正丁基锡和二乙基锡单氟苯甲酸盐：合成、光谱表征和体外抗肿瘤活性
影响因子：
3.9
作者：
M. Gielen;A. E. Khloufi;M. Biesemans,;R. Willem,
通讯作者：
R. Willem,
不稳定顺式二烷氧基双(乙酰丙酮)钛(IV)化合物的核磁共振和红外光谱研究
DOI：
10.1039/j19690000282
发表时间：
1969
期刊：
Journal of The Chemical Society A: Inorganic, Physical, Theoretical
影响因子：
--
作者：
D. C. Bradley;C. Holloway
通讯作者：
C. Holloway