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A Modular Approach to Carbene-Stabilized Diphosphorus Species

A Modular Approach to Carbene-Stabilized Diphosphorus Species

Adinarayana Doddi, Dirk Bockfeld, Marc-Kevin Zaretzke, Christian Kleeberg, Thomas Bannenberg, Matthias Tamm

Dalton Trans. 2017 Nov 21;46(45):15859-15864.

PMID: 29114655

Abstract:

Heteroleptic N-heterocyclic dicarbene-diphosphorus species were prepared by reaction of the carbene-phosphinidene adduct (IPr)PSiMe3 (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with the carbene-phosphorus trichloride adduct (IMes)PCl3 (2, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene), which furnished the dichloride [(IPr)PPCl(IMes)]Cl (3). Reduction of 3 with potassium graphite (KC8) afforded [(IPr)PP(IMes)] (4). The corresponding radical cation [(IPr)PP(IMes)]˙+ (5˙+) is isolated as [5]PF6 by reaction of 4 with ferrocenium hexafluorophosphate, whereas complexes containing the corresponding dication [(IPr)PP(IMes)]2+ (62+) can be isolated as the gallate and borate salts [6](GaCl4)2 and [6](BArF)2 by chloride abstraction from 3 with GaCl3 or sodium tetrakis[bis(3,5-trifluoromethyl)phenyl]borate (NaBArF), respectively. The asymmetric set of N-heterocyclic carbene ligands allows to establish 1JPP coupling constants of 249 Hz for 4 and 543 Hz for [6](GaCl4)2. Based on X-ray diffraction analyses, the molecular structures of 4, 5˙+ and 62+ reveal a consecutive shortening of the P-P bond lengths, in agreement with the presence of a phosphorus-phosphorus single bond in 4 and a double bond in 62+, which is best described as a dicationic diphosphene according to density functional theory (DFT) calculations.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP105560529	Potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate		105560-52-9	Price
AP79060881	Sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate		79060-88-1	Price

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