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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)(3)}](+) via the redox activation of scorpionate complexes [RhLL ' Tt]
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A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)(3)}](+) via the redox activation of scorpionate complexes [RhLL ' Tt]

机译：一种通过蝎形配合物[RhLL'Tt]的氧化还原激活而获得罗丹硼烷的新途径[Rh（CO）（PR3）{B（taz）（3）}]（+）

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摘要

The reaction of a mixture of the sodium salts of dihydrobis(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate, NaBt, and hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate, NaTt, with [{Rh(cod)(mu-Cl)}(2)] gave [Rh(cod)Bt] and [Rh(cod)Tt], which separately react with CO gas to give the unstable dicarbonyl [Rh(CO)(2)Bt] and an equilibrium mixture of two isomers of [Rh(CO)(2)Tt] and [(RhTt)(2)(mu-CO)(3)], respectively. Tertiary phosphorus donor ligands react with the mixture of [Rh(CO)(2)Tt] and [(RhTt)(2)(mu-CO)(3)] to give [Rh(CO)(PR3)Tt] (R = Cy, NMe2, Ph or OPh) and [Rh{P(OPh)(3)}(2)Tt] in which rhodium is bound to two sulfur atoms of the scorpionate ligand; the B-H bond is directed towards the metal to give an agostic-like B-H center dot center dot center dot Rh interaction. Dinuclear [(RhTt)(2)(mu-CO)(3)] has kappa(3)[S-3]-bound Tt ligands with a rhodium-rhodium bond bridged by three carbonyls. In solution the mononuclear Tt complexes undergo rapid dynamic interchange of the three thioxotriazolyl rings, probably via kappa(3)[S-3]-coordinated intermediates. The monocarbonyls [Rh(CO)(PR3)Tt] (R = Cy, NMe2 or Ph) react with two equivalents of [Fe(eta-C5H5)(2)][PF6] in the presence of triethylamine to give the monocationic rhodaboratranes [Rh(CO)(PR3){B(taz)(3)}](+), with boron NMR spectroscopy providing evidence for the boron-rhodium bond. In the solid state, rhodium is bound to the three sulfur atoms and the boron of the B(taz)(3) fragment, forming a tricyclo[3.3.3.0] cage. The phosphine is trans to the Rh-B bond, the long Rh-P bond indicating a pronounced trans influence for the coordinated boron. The cation [Rh(CO)(PPh3){B(taz)(3)}](+) reacts with [NBu4n]I to give [Rh(PPh3)I{B(taz)(3)}], in which the halide is trans to the Rh-B bond, and a second species, possibly [Rh(CO)I{B(taz)(3)}]. The dirhodaboratrane [Rh-2(PCy3){B(taz)(3)}(2)][PF6](2), a minor byproduct in the synthesis of [Rh(CO)(PCy3){B(taz)(3)}][PF6], has a distorted square pyramidal rhodium atom with a vacant site trans to the Rh-B bond. The second metal has four coordination sites filled by the sulfur and boron atoms of a second B(taz)(3) unit, the remaining octahedral sites occupied by two of the sulfur atoms of the first B(taz)(3) unit which therefore bridges the two rhodium atoms.
机译：二氢双（4-乙基-3-甲基-5-硫代-1,2,4-三唑基）硼酸钠盐，NaBt和氢三（4-乙基-3-甲基-5-硫代）的反应-1,2,4-三唑基）硼酸钠NaTt与[{Rh（cod）（mu-Cl）}（2）]得到[Rh（cod）Bt]和[Rh（cod）Tt]，它们分别反应用一氧化碳气体产生不稳定的二羰基[Rh（CO）（2）Bt]和[Rh（CO）（2）Tt]和[（RhTt）（2）（mu-CO）（ 3）]。叔磷供体配体与[Rh（CO）（2）Tt]和[（RhTt）（2）（mu-CO）（3）]的混合物反应，得到[Rh（CO）（PR3）Tt]（R ＝ Cy，NMe 2，Ph或OPh）和[Rh {P（OPh）（3）}（2）Tt]，其中铑与蝎状配体的两个硫原子结合; B-H键指向金属，以产生类似B-H中心点的圆弧状。双核[（RhTt）（2）（mu-CO）（3）]具有与由三个羰基桥接的铑-铑键的κ（3）[S-3]结合的Tt配体。在溶液中，单核Tt配合物可能通过kappa（3）[S-3]配位的中间体快速经历三个thioxotriazolyl环的动态互换。在三乙胺的存在下，单羰基[Rh（CO）（PR3）Tt]（R = Cy，NMe2或Ph）与两当量的[Fe（eta-C5H5）（2）] [PF6]反应，得到单阳离子Rhodaboratranes [Rh（CO）（PR3）{B（taz）（3）}]（+），具有硼NMR光谱学，提供了硼铑键的证据。在固态状态下，铑与三个硫原子和B（taz）（3）片段的硼键合，形成三环[3.3.3.0]笼。膦与Rh-B键形成反式，较长的Rh-P键表明对配位硼有明显的反式影响。阳离子[Rh（CO）（PPh3）{B（taz）（3）}]（+）与[NBu4n] I反应生成[Rh（PPh3）I {B（taz）（3）}]，其中卤化物被反式连接到Rh-B键上，第二种可能是[Rh（CO）I {B（taz）（3）}]。 dirhodaboratrane [Rh-2（PCy3）{B（taz）（3）}（2）] [PF6]（2），[Rh（CO）（PCy3）{B（taz）（ 3）}] [PF6]，具有扭曲的方形金字塔形铑原子，其空位反式至Rh-B键。第二种金属具有四个配位点，由第二个B（taz）（3）单元的硫和硼原子填充，其余八面体位点由第一个B（taz）（3）单元的两个硫原子占据，因此桥接两个铑原子。

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