Metal promoted charge and hapticities of phosphines: The uniqueness of carboranylphosphines

Popescu, Adrian; Teixidor, Francesç; Viñas, Clara

doi:10.1016/j.ccr.2014.02.016

Cited by 94 publications

(47 citation statements)

References 170 publications

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“…The P O B complex 76 was found to be much more active than its P B and P O C counterparts 75 and [RhCl( i Pr 2 POPh)(1,5-cod)] in hydrolsilylation. In hydroboration, similar activities were observed Ligands with carborane substituents are known for a variety of donor atoms [82,83]. The bonding properties of these carboranyl ligands are strongly dependent on the vertex to which the donor atom is bonded [84,85].…”

Section: Rhodium Complexesmentioning

confidence: 54%

Monomeric phosphinoboranes

Bailey

Pringle

2015

Coordination Chemistry Reviews

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Section: Rhodium Complexesmentioning

confidence: 54%

Monomeric phosphinoboranes

Bailey

Pringle

2015

Coordination Chemistry Reviews

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“…Compared to this bisphosphane, 8‐ trans presents an even longer C cluster −C cluster bond (1.803(2) Å vs. 1.760(4) Å) . Elongated C−C bond lengths are commonly observed in carborane‐substituted phosphanes and bisphosphanes and are indicative of backbonding of the lone pair of electrons on phosphorus to the carborane cluster …”

Section: Resultsmentioning

confidence: 95%

Exploiting the Ring Strain of Diphosphetanes: A Synthetic and Computational Approach towards 1,2,5‐Selenadiphospholanes

et al. 2018

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A carboranyl‐based meso‐1,2,5‐selenadiphospholane diselenide was synthesised starting from a strained carborane‐substituted 1,2‐diphosphetane and subsequently reduced to an unprecedented carboranyl‐based meso‐1,2,5‐selenadiphospholane. The electronic structure and the bonding situation for both compounds were investigated by density functional theory (DFT), Natural Bond Orbital (NBO) analyses, Fractional Occupation Density (FOD) analysis, Complete Active Space Self Consistent Field (CASSCF) calculations and time‐dependent DFT (TDDFT) calculations. Ring‐opening reactions of meso‐1,2,5‐selenadiphospholane with nucleophiles and electrophiles are reported together with calculated reaction mechanisms (DFT level). Isolated compounds were characterised by NMR and IR spectroscopy, high‐resolution mass spectrometry, elemental analysis and single‐crystal X‐ray diffraction.

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“… Literature‐known and new strategies for the syntheses of nido ‐carborane‐substituted phosphane ligands and complexes.…”

Section: Introductionmentioning

confidence: 99%

Accessing the First nido‐Carborane‐Substituted Diphosphetane: A Ligand and Synthon for nido‐Carboranylphosphanes

Coburger

Bielytskyi

Williamson

et al. 2019

Chemistry A European J

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Deboronation of a carborane‐substituted diphosphetane 2 in toluene yielded the first nido‐carboranyldiphosphetane 1. The P−P bond in 1 can be broken via dismutation reactions with diaryl dichalcogenides yielding nido‐carboranyl bis‐phosphanes that were not accessible via established synthetic protocols. Additionally, transition metal complexes of 1 could be isolated including one coordination polymer. Notably, when the deboronation of 2 is carried out in ethanol, unprecedented nido‐carborane‐substituted secondary bis‐phosphane monoxides (3, 4) are obtained. These compounds are interesting starting materials for further reactivity studies due to their P−H bonds. Experimental findings are supported by DFT calculations including the calculation of reaction mechanisms and NMR spectroscopic parameters.

show abstract

Metal promoted charge and hapticities of phosphines: The uniqueness of carboranylphosphines

Cited by 94 publications

References 170 publications

Monomeric phosphinoboranes

Monomeric phosphinoboranes

Exploiting the Ring Strain of Diphosphetanes: A Synthetic and Computational Approach towards 1,2,5‐Selenadiphospholanes

Accessing the First nido‐Carborane‐Substituted Diphosphetane: A Ligand and Synthon for nido‐Carboranylphosphanes

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