Syntheses and Structures of Group 10 Metal POCOP Pincer Complexes Bearing A Mercapto‐<i>o–</i>carborane Auxiliary Ligand

Zhang, Jie; Cao, Bula; Ding, Yazhou; Chang, Jiarui; Li, Shujun; Chen, Xuenian

doi:10.1002/slct.201803908

Cited by 7 publications

(2 citation statements)

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“…In contrast to other MOCHA materials with an extended metal chalcogenide core, MicroED has revealed that the synthesized carborane-structured MOCHAs consist of an unprecedented zero-dimensional Cu 4 Se 4 cluster that is representative of the smallest building block of bulk CuSe materials. This work therefore further establishes the utility of MicroED for hybrid material structure elucidation when reaching the limitations of more traditional structural determination methods. − This study furthermore highlights how the use of bulky, organomimetic, boron cluster ligands can lead to the formation of hybrid materials with unique structures and properties. − ,− ,− …”

Section: Discussionmentioning

confidence: 64%

“…Carboranes, with the molecular formula of C 2 B 10 H 12 , exist as three distinct isomers ( ortho -, meta -, para -) distinguished by the relative orientation of the two carbon vertices. Importantly, the electronic nonuniformity of ortho - and meta -carboranes, resulting from the asymmetry introduced by the carbon vertices, has allowed for the precise modulation of metal surface − and metal center properties, − as determined by the relative positioning of ligating substituents on the sterically invariant boron clusters (Figure b). This electronic nonuniformity is further exemplified by the regioselective chemistry of carboranes that has permitted selective introduction of functional groups to the carbon-based vertices and various boron-based vertices of carboranes. − …”

Section: Introductionmentioning

confidence: 99%

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Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

et al. 2022

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Herein, we report the use of sterically invariant carborane-based chalcogenols, containing exopolyhedral B-Se or B-S bonds, as ligands for the formation of photoluminescent copper(I)based metal-organic chalcogenolate assemblies (MOCHAs). We show that precise tuning of the carborane dipole by changing the carborane isomer from meta-to ortho-allows for control over the MOCHA morphology and regulation of the resulting photophysical properties. Furthermore, microcrystal electron diffraction (MicroED) has been demonstrated as a powerful tool for metal chalcogenide structure elucidation. Through the use of MicroED, one of the isolated materials is determined to consist of zero-dimensional Cu 4 (Se-C 2 B 10 H 11 ) 4 clusters with an unprecedented Cu 4 Se 4 geometry.

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Section: Discussionmentioning

confidence: 64%

Section: Introductionmentioning

confidence: 99%

Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

et al. 2022

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Hydrosilylation of Aldehydes and Ketones Catalysed by Bis(phosphinite) Pincer Platinum Hydride Complexes

et al. 2020

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Bis(phosphinite) pincer platinum hydride complexes, [2,6‐(R2PO)2C6H3]PtH (R=tBu, iPr), were synthesized, characterized and applied to the hydrosilylation of aldehydes and ketones. NMR study and single crystal X‐ray diffraction analysis indicated that the hydrides in these two platinum complexes are comparatively less hydridic: down‐field 1H NMR resonances (0.71 and 0.98 ppm) and weak Pt−H interactions were observed. Both the platinum complexes were found to be good catalysts for the hydrosilylation of aldehydes and ketones with phenylsilane. The corresponding alcohols were isolated in good to excellent yields following basic hydrolysis of the resultant hydrosilylation products and turnover frequencies (TOFs) up to 3200 h−1 were achieved at 60 °C in toluene, which are much higher than those of the hydrosilylation catalysed by the corresponding nickel pincer hydride complexes. A possible mechanism for the present hydrosilylation process was discussed.magnified image

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A Structure Comparison of Ni(II) Complexes Supported by PNCNP and POCOP Pincer Ligands

et al. 2020

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In order to compare the structure and property of the same metal center supported by different types of pincer ligands, a series of Ni(II) pincer complexes, [2,6‐(iPr2PNH)2C6H3]NiX (X=SH, 1 a; SPh, 1 b; SBn, 1 c; BH4, 1 d), were synthesized based on m‐(iPr2PNH)2C6H4 (PNCNP) and fully characterized by multinuclear NMR, FTIR, X‐ray crystallography and elemental analysis. The structures of complexes 1 a–d were compared with those of the corresponding Ni(II) complexes supported by a bis(phosphinite) (POCOP) pincer ligand, [2,6‐(iPr2PO)2C6H3]NiX (X=SH, 2 a; SPh, 2 b; SBn, 2 c; BH4, 2 d). It was found that the Ni‐Cipso and Ni−S bond lengths and the Ni⋅⋅⋅B distance in complexes 1 a–d are comparable to those in complexes 2 a–d; however, the Ni−P bond lengths in complexes 1 a–d are longer than those in complexes 2 a–d. As a result, the nickel center is less tightly chelated by the PNCNP backbone compared with the POCOP framework. Natural population analysis (NPA) of complexes 1 a, 2 a, 1 b and 2 b indicated that the nickel center supported by a PNCNP pincer ligand is less electron‐rich. Cyclic voltammetry study of 1 a and 2 a showed that 2 a is easier to be oxidized.

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Syntheses and Structures of Group 10 Metal POCOP Pincer Complexes Bearing A Mercapto‐o–carborane Auxiliary Ligand

Cited by 7 publications

References 97 publications

Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

Hydrosilylation of Aldehydes and Ketones Catalysed by Bis(phosphinite) Pincer Platinum Hydride Complexes

A Structure Comparison of Ni(II) Complexes Supported by PNCNP and POCOP Pincer Ligands

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