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首页> 外文期刊>Zeitschrift fur Naturforschung, B. A Journal of Chemical Sciences >Functionalization of 1,3-diphosphacyclobutadiene cobalt complexes via Si–P bond insertion
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Functionalization of 1,3-diphosphacyclobutadiene cobalt complexes via Si–P bond insertion

机译：通过Si-P键粘合剂的1,3-二磷算法钴配合物的官能化

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摘要

We report the synthesis of functionalized 1,3-bis(diphosphacyclobutadiene) complexes via the insertion of carbon-oxygen bonds of ethers, esters, aldehydes and amides into the P–Si bond of silylated complexes. Reactions of [K(tol)2][Co(η4-P2C2R2)2] [[K(tol)2][1a]: R=tBu, [K(tol)2][1b]: R=tPent (=tert-pentyl)] with Me3SiCl afford the trimethylsilyl-substituted derivatives [Co(η4-P2C2R2SiMe3)(η4-P2C2R2)] (2a,b, R=tBu, tPent). The Me3Si group is connected to a phosphorus atom of one of the 1,3-diphosphacyclobutadiene ligands. 2a,b readily react with organic substrates containing C–O single and C=O double bonds at ambient temperature. [Co(η4-P2C2R2(CH2)4OSiMe3)(η4-P2C2R2)] (3a, b) are formed by reaction of 2a, b with traces of THF. They can also be isolated by reacting the THF solvates [K(thf)2{Co(P2C2tBu2)2}] ([K(thf)2][1a]) and [K(thf)3{Co(P2C2tPent2)2}] ([K(thf)3][1b]) with Me3SiCl in toluene or THF. The adamantyl-substituted complex [Co(η4-P2C2Ad2(CH2)4OSiMe3)(η4-P2C2Ad2)] (3c) was prepared analogously from [K(thf)4{Co(P2C2Ad2)2}] and Me3SiCl. [K(thf)2][1a] reacts cleanly with Ph3SnCl affording [Co(η4-P2C2tBu2SnPh3)(η4-P2C2tBu2)] (4) in high yield. Reaction of 2a with styrene oxide affords [Co(η4-P2C2tBu2PhC2H3OSiMe3)(η4-P2C2tBu2)] (5) as a single regioisomer. By contrast, multinuclear NMR spectroscopic studies indicate mixtures of two isomeric insertion products 6/6′ and 7/7′, respectively, which result from the insertion of 1,2-epoxy-2-methylpropane and 1,2-epoxyoctane. Moreover, these monitoring studies show that reactions of 2a with acyclic ethers afford alkyl substituted complexes such as [Co(η4-P2C2tBu2Et)(η4-P2C2tBu2)] (8) and alkylsilyl ethers. Reaction of 2a with γ-butyrolactone gives [Co(η4-P2C2tBu2(CH2)3C(O)OSiMe3)(η4-P2C2tBu2)] (9) via cleavage of the endocyclic C–O single bond of the lactone. Benzaldehyde and acetone cleanly react with 2a to [Co(η4-P2C2tBu2CH(Ph)OSiMe3)(η4-P2C2tBu2)] (10) and [Co(η4-P2C2tBu2CMe2OSiMe3)(η4-P2C2tBu2)] (11), while the sterically more demanding ketones 3-pentanone and acetophenone selectively yield the known hydride complex [Co(η4-P2C2tBu2)2H] (A). Phenyl isocyanate reacts with 2a at elevated temperature to form [Co(η3-P2C2tBu2CON(Ph)SiMe3)(η4-P2C2tBu2)] (12) with a functionalized η3-coordinated ligand. [K(tol)2][1a], [K(tol)2][1b], 2a, 2b, 3a–c, 4, 5, and 9–12 were isolated and characterized by multinuclear NMR spectroscopy, UV/Vis spectroscopy and elemental analysis. [K(tol)2][1b], 2a, 2b, 3c, 4, 5, and 9–12 were additionally characterized by X-ray crystallography.
机译：我们通过将醚，酯，醛和酰胺的碳 - 氧键插入甲硅烷基化合物的P-Si键的碳 - 氧键，通过插入官能化1,3-双（二磷酸盐丁二烯）复合物的合成。 [k（tol）2] [co（η4-p2c2r2）2] [[k（tol）2] [1a]：r = tbu，[k（tol）2] [1b]：r = tpent（=叔戊基）]用ME3SICL提供三甲基甲硅烷基取代的衍生物[CO（η4-p2c2sime3）（η4-p2c2r2）]（2a，b，r = tbu，tpent）。 ME3SI组连接到1,3-二磷酸盐丁二烯配体之一的磷原子。如图2A所示，B容易与在环境温度下含有C-O单和C = O双键的有机底物反应。 [Co（η4-P2C2R2（CH2）4透明度3）（η4-P2C2R2）]（3a，b）通过2a，b与THF的痕量反应形成。还可以通过使THF溶剂化物[K（THF）2 {CO（P2C2TBU2）2}]反应分离来分离它们。（[k（THF）2] [1A]）和[K（THF）3 {CO（P2C2TPENT2）2}用ME3SICL在甲苯或THF中的[K（THF）3] [1B]）。与[K（THF）4 {CO（P2C2AD2）2}]和ME3SICL类似地制备金刚烷基取代的复合物[CO（η4-P2C2AD2（CH2）4℃）（3C）。 [k（THF）2] [1A]用高产率的pH3SNCL与pH3SNCL合带[CO（η4-P2c2TBU2SNPH3）（4），与pH3SNCL合带反应。 2a与苯乙烯氧化物的反应得到[CO（η4-p2c2phc2ph37Sime3）（η4-p2c2tbu2）]（5）作为单个测定剂。相比之下，多核NMR光谱研究表明，两种异构插入产物6/6'和7/7'的混合物，这是由1,2-环氧-2-甲基丙烷和1,2-环氧辛烷的插入引起的。此外，这些监测研究表明，2A与无循环醚的反应提供烷基取代的配合物，例如[CO（η4-P2C2TBU2ET）（η4-P2C2TBU2）]（8）和烷基甲硅烷基醚。 2a与γ-丁内酯的反应得到γ-（η4-p2c2tbu2（ch 2）3c（o）osime3）（η4-p2c2tbu2）]（9）通过内环c-o单键的内环c-o单键粘合。苯甲醛和丙酮干净地与2a至[co（η4-p2c2tbu2ch（pH）osime3）（η4-p2c2tbu2）]（10）和[co（η4-p2c2tbu2cme2sosime3）（η4-p2c2tbu2）]（11），而在空间上更多要求酮3-戊酮和苯乙酮选择性地产生已知的氢化物络合物[CO（η4-P2C2TBU2）2H]（A）。苯基异氰酸酯在升高的温度下与2A反应，以形成官能化η3配位配体的[CO（η3-P2C2CON（pH）SIME3）（η4-P2C2TBU2）]（12）。 [k（tol）2] [1a]，[k（tol）2] [1b]，2a，2b，3a-c，4,5和9-12被多核NMR光谱，UV / Vis表征光谱学和元素分析。 [k（tol）2] [1B]，2A，2B，3C，4,5和9-12通过X射线晶体学表征。

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