Steric versus electronic factors in metallacarborane isomerisation: nickelacarboranes with 3,1,2-, 4,1,2- and 2,1,8-NiC2B9 architectures and pendant carborane groups, derived from 1,1'-bis(o-carborane).

Steric versus electronic factors in metallacarborane isomerisation: nickelacarboranes with 3,1,2-, 4,1,2- and 2,1,8-NiC2B9 architectures and pendant carborane groups, derived from 1,1'-bis(o-carborane).
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金属碳硼烷异构化中的空间因素与电子因素:具有 3,1,2-、4,1,2- 和 2,1,8-NiC2B9 结构的镍碳硼烷以及衍生自 1,1-双(邻碳硼烷)的碳硼烷侧基

DOI:
10.1039/c6dt02855a
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发表时间:
2016
期刊:
2003)
影响因子:
--
通讯作者:
Mandal D
Mandal D
中科院分区:
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文献类型:
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作者:
Mandal D

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[7-(1 ' -1 ',2 ' - clo索- c2b10h11)-7,8-nido- c2b9h10]2−二离子与各种{nippp2 +}或{NiP22+}片段(PP =螯合二膦;P =单齿膦或亚磷酸盐)的金属化可以得到异构化的3,1,2- nic2b9或异构化的4,1,2- nic2b9或2,1,8- nic2b9,所有这些都有一个悬垂的C2B10取代基。产品[1 - (1 ' 1 ',2 ' -closo-C2B10H11) 3-dppe-3 1 2-closo-NiC2B9H10] (1), (2 - (1 ' 1 ', 2 ' -closo-C2B10H11) 4-dppe-4 1 2-closo-NiC2B9H10] (2), (8 - (1 ' 1 ', 2 ' -closo-C2B10H11) 2-dmpe-2 1 8-closo-NiC2B9H10) (3), (1 - (1 ' 1 ', 2 ' -closo-C2B10H11) 3, 3 - (PMe3) 2 - 3, 1, 2-closo-NiC2B9H10] (4), (1 - (1 ' 1 ', 2 ' -closo-C2B10H11) 3, 3 - (PMe2Ph) 2 - 3, 1, 2-closo-NiC2B9H10) (6),[1-(1 ' -1 ',2 ' -closo- c2b10h11)-3,3-{P(OMe)3}2-3,1,2-closo- nic2b9h10](9)和[1-(1 ' -1 ',2 ' -closo- c2b10h11)-2,2- closo- nic2b9h10](10)进行了光谱和晶体学表征,而[2-(1 ' -1 ',2 ' -closo- c2b10h11)-4,4-(PMePh2)2-4,1 -closo- nic2b9h10](8)进行了光谱表征。总的来说,结果表明,3,1,2至4,1,2异构化的一个重要因素是空间拥挤带来的缓解,而3,1,2至2,1,8异构化似乎有利于金属上的强电子给体配体。
Metalation of the [7-(1′-1′,2′-closo-C2B10H11)-7,8-nido-C2B9H10]2− dianion with various {NiPP2+} or {NiP22+} fragments (PP = chelating diphosphine; P = monodentate phosphine or phosphite) leads either to unisomerised 3,1,2-NiC2B9 species or to isomerised 4,1,2-NiC2B9 or 2,1,8-NiC2B9 species, all with a pendant C2B10 substituent. The products [1-(1′-1′,2′-closo-C2B10H11)-3-dppe-3,1,2-closo-NiC2B9H10] (1), [2-(1′-1′,2′-closo-C2B10H11)-4-dppe-4,1,2-closo-NiC2B9H10] (2), [8-(1′-1′,2′-closo-C2B10H11)-2-dmpe-2,1,8-closo-NiC2B9H10] (3), [1-(1′-1′,2′-closo-C2B10H11)-3,3-(PMe3)2-3,1,2-closo-NiC2B9H10] (4), [1-(1′-1′,2′-closo-C2B10H11)-3,3-(PMe2Ph)2-3,1,2-closo-NiC2B9H10] (6), [1-(1′-1′,2′-closo-C2B10H11)-3,3-{P(OMe)3}2-3,1,2-closo-NiC2B9H10] (9) and [1-(1′-1′,2′-closo-C2B10H11)-2,2-{P(OMe)3}2-2,1,8-closo-NiC2B9H10] (10) were fully characterised spectroscopically and crystallographically, whilst [2-(1′-1′,2′-closo-C2B10H11)-4,4-(PMePh2)2-4,1,2-closo-NiC2B9H10] (8) was characterised spectroscopically. Overall the results suggest that an important factor in a 3,1,2 to 4,1,2 isomerisation is the relief gained from steric crowding, whereas a 3,1,2 to 2,1,8 isomerisation appears to be favoured by strongly electron-donating ligands on the metal.
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