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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Diphosphanes derived from phobane and phosphatrioxa-adamantane: Similarities, differences and anomalies
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Diphosphanes derived from phobane and phosphatrioxa-adamantane: Similarities, differences and anomalies

机译：衍生自膦烷和三氧杂磷金刚烷的二膦烷：异同和异常

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The homodiphosphanes CgP-PCg (1) and PhobP-PPhob (2) and the heterodiphosphanes CgP-PPhob (3), CgP-PPh_2 (4a), CgP-P(o-Tol) _2 (4b), CgP-PCy_2 (4c), CgP-PtBu_2 (4d), PhobP-PPh_2 (5a), PhobP-P(o-Tol)_2 (5b), PhobP-PCy_2 (5c), PhobP-PtBu2 (5d) where CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl and PhobP = 9-phosphabicyclo[3.3.1]nonan-9-yl have been prepared from CgP(BH3)Li or PhobP(BH_3)Li and the appropriate halophosphine. The formation of 1 is remarkably diastereoselective, with the major isomer (97% of the product) assigned to rac-1. Restricted rotation about the P-P bond of the bulky meso-1 is detected by variable temperature 31P NMR spectroscopy. Diphosphane 3 reacts with BH3 to give a mixture of CgP(BH_3)-PPhob and CgP-PPhob(BH_3) which was unexpected in view of the predicted much greater electron-richness of the PhobP site. Each of the diphosphanes was treated with dimethylacetylene dicarboxylate (DMAD) in order to determine their propensity for diphosphination. The homodiphosphanes 1 and 2 did not react with DMAD. The CgP-containing heterodiphosphanes 4a-d all added to DMAD to generate the corresponding cis alkenes CgPCH(CO_2Me)CH(CO_2Me)PR _2 (6a-d) which have been used in situ to form chelate complexes of the type [MCl2(diphos)] (7a-d) where M = Pd or Pt. The PhobP-containing heterodiphosphanes 3 and 5a-d react anomalously with DMAD and do not give the products of diphosphination. The X-ray crystal structures of the diphosphanes 2, 3, 4a, and 5a, the monoxide and dioxide of diphosphane 1, and the platinum chelate complex 7c have been determined and their structures are discussed.
机译：均二膦CgP-PCg（1）和PhobP-PPhob（2）和杂二膦CgP-PPhob（3），CgP-PPh_2（4a），CgP-P（o-Tol）_2（4b），CgP-PCy_2（4c） ），CgP-PtBu_2（4d），PhobP-PPh_2（5a），PhobP-P（o-Tol）_2（5b），PhobP-PCy_2（5c），PhobP-PtBu2（5d）其中CgP = 6-phospha-2由CgP（BH3）Li或PhobP（BH_3）制备了1,4,8-三氧杂-1,3,5,7-四甲基金刚烷基-9-基和PhobP = 9-磷酸双环[3.3.1] nonan-9-基李和适当的卤代膦。 1的形成具有非对映选择性，主要异构体（占产品的97％）分配给rac-1。通过可变温度31 P NMR光谱检测到大体积meso-1的P-P键周围的旋转受限。二膦3与BH3反应生成CgP（BH_3）-PPhob和CgP-PPhob（BH_3）的混合物，鉴于PhobP位点的电子富集度更高，这是出乎意料的。为了确定它们的二磷酸化倾向，将每个二膦用二甲基乙炔二羧酸酯（DMAD）处理。均二膦1和2不与DMAD反应。含CGP-heterodiphosphanes图4a-d全部加到DMAD以产生烯烃CgPCH（CO_2Me）CH（CO_2Me）PR _2（图6a-d）的相应的顺式已在原位被用于形成型的螯合络合物[MCL2（DIPHOS ）]（7a-d），其中M = Pd或Pt。含PhobP的杂二膦3和5a-d与DMAD异常反应，不会产生二磷酸化产物。已经确定了二膦2、3、4a和5a的X射线晶体结构，二膦1的一氧化碳和二氧化物以及铂螯合物7c，并对其结构进行了讨论。

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