Synthesis of a Cyclic Co2Sn2 Cluster Using a Co– Synthon

Hoidn, Christian M.; Rödl, Christian; McCrea-Hendrick, Madison L.; Block, Theresa; Pöttgen, Rainer; Ehlers, Andreas W.; Power, Philip P.; Wolf, Robert

doi:10.1021/jacs.8b08517

Cited by 24 publications

(29 citation statements)

References 71 publications

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“…By contrast, a previously reported, related cluster compound (Ar′SnCo)2 features strong covalent Sn-Co bonds, which even have partial multiple bond character. 12 It is noteworthy that although the Tt-Co and Tt-P distances for 1-3 increase down the group, the bond angles are approximately the same (C1-Tt-Co1 127°-129°, C1-Tt-P1 102°-103°). As a consequence of the relatively short atomic radius of germanium, the terphenyl substituent and the Co(P2C2tBu2)(COD) unit in 1 are very close to each other resulting in a restricted rotation of the terphenyl ligand around the Tt-P/Tt-C bonds as evidenced by variable temperature (VT) NMR experiments.…”

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confidence: 90%

“…A recent work from our group has successfully utilised the reaction of white phosphorus (P4) with heterobimetallic complexes to prepare unusual polyphosphorus compounds. 12,13 Using this strategy, we have now synthesised the heavy tetraphospholide anions SnP4 2− and PbP4 2− . These hitherto unknown -aromatic molecules are stabilised by the coordination to two cobalt atoms in the triple-decker sandwich compounds [(η 4 -tBu2C2P2)2Co2(μ,η 5 :η 5 -P4Tt)] [Tt = Sn (6), Pb (7)].…”

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confidence: 99%

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Transition-Metal-Stabilised Heavy Tetraphospholide Anions

Kelly

Streitferdt

Dimitrova

et al. 2022

Preprint

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Phosphorus analogues of the ubiquitous cyclopentadienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heaviear group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopen-tadienyl anions (SnP4)2─ and (PbP4)2─. The complexes [(η4-tBu2C2P2)2Co2(μ,η5:η5-P4Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P4) with cyclooctadiene cobalt complexes [Ar′TtCo(η4-P2C2tBu2)(η4-COD)] [Sn (2), Pb (3), Ar′ = C6H3-2,6{C6H3¬-2,6-iPr2}2, COD = cycloocta-1,5-diene] and Tt{Co(η4-P2C2tBu2)(COD)}2 [Tt = Sn (4), Pb (5)]. While the (SnP4)2− complex 6 was isolated as a pure and stable compound, compound 7 eliminates Pb(0) below room temper-ature to afford [(η4-tBu2C2P2)2Co2(μ,η4:η4-P4) (8), which is a rare example of a tripledecker complex with a (P4)2─ middle deck. The electronic structures of 6-8 are analysed using theoretical methods, including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby the aromatic nature of (P5)− and (SnP4)2− was confirmed, while for (P4)2− a specific type of symmetry-induced weak paramagnetism was found which is distinct from conventional antiaromatic species.

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Transition-Metal-Stabilised Heavy Tetraphospholide Anions

Kelly

Streitferdt

Dimitrova

et al. 2022

Preprint

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“…More recently, a joint study by Power, Wolf and co‐workers demonstrated that the low‐coordinate cobalt‐tin cluster 14 serves as a potent agent for one‐step P 4 activation and functionalization (Scheme 5 a). [18] During the reaction, the P 4 tetrahedron is selectively inserted into the rhombohedral Co 2 Sn 2 cluster core of 14 , during which one of the bulky, tin‐bound terphenyl substituents undergoes a migration to phosphorus, thereby forming a new P−C bond. The product 15 bears a terphenyl‐substituted P 4 chain and represented the first example of a molecular cluster compound containing phosphorus, cobalt and tin.…”

Section: Transition‐metal‐mediated Functionalization Of White Phosphorusmentioning

confidence: 99%

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Hoidn

Scott

Wolf

2020

Chemistry A European J

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Recently there has been great interest in the reactivity of transition‐metal (TM) centers towards white phosphorus (P4). This has ultimately been motivated by a desire to find TM‐mediated alternatives to the current industrial routes used to transform P4 into myriad useful P‐containing products, which are typically indirect, wasteful, and highly hazardous. Such a TM‐mediated process can be divided into two steps: activation of P4 to generate a polyphosphorus complex TM‐Pn, and subsequent functionalization of this complex to release the desired phosphorus‐containing product. The former step has by now become well established, allowing the isolation of many different TM‐Pn products. In contrast, productive functionalization of these complexes has proven extremely challenging and has been achieved only in a relative handful of cases. In this review we provide a comprehensive summary of successful TM‐Pn functionalization reactions, where TM‐Pn must be accessible by reaction of a TM precursor with P4. We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry.

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“…Steric shielding around the tetrel site has also been widely exploited as a strategy to provide kinetic stabilization, being terphenyl (C6H3-2,6-Ar2) substituents among the preferred choice. 30 In fact, coordination of terphenyl-stabilized tetrylenes to transition metals has already provided compelling results, [31][32][33][34][35][36][37] revealing the tunable donor/acceptor nature of the group 14 element 38,39 and the realization of its highly dynamic binding capacity. [40][41][42][43][44][45] For instance, the interconversion with tetrylidyne (M≡E-R) and tetryl (M-ER3) forms drastically modify the bonding with the transition metal and its stereoelectronic properties, producing reactive unsaturated sites amenable for divergent reactivity.…”

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Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

Bajo¹,

Alcaide²,

López-Serrano³

et al. 2021

Preprint

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Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.

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Synthesis of a Cyclic Co₂Sn₂ Cluster Using a Co^– Synthon

Cited by 24 publications

References 71 publications

Transition-Metal-Stabilised Heavy Tetraphospholide Anions

Transition-Metal-Stabilised Heavy Tetraphospholide Anions

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

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