Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η2-Coordination Mode between Ruthenium(0) and a Phosphaalkene

Autor:	Alex Sergey Ionkin, Dalen E. Keys, Fredric Davidson, Charles N. McEwen, William J. Marshall, Brian M. Fish, Matthew F. Schiffhauer
Rok vydání:	2007
Předmět:	Chemical shift Organic Chemistry Ring (chemistry) Photochemistry Inorganic Chemistry chemistry.chemical_compound Delocalized electron Crystallography Molecular geometry chemistry Dehydrohalogenation Phosphaalkene Single bond Physical and Theoretical Chemistry Lone pair
Zdroj:	Organometallics. 26:5050-5058
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om7005084
Popis:	1-(2,4,6-Tri-tert-butylphenyl)-1H-[1,2]diphosphole (12) was isolated from the unintentional and unexpected dehydrohalogenation of 1,3-bis(chloro(2,4,6-tri-tert-butylphenyl)phosphino)propane (5) with DBN. 1H-[1,2]Diphosphole 12 has substantial bond delocalization within the diphosphole system. Remarkably, the shortest P−C bond in the ring (1.725(4) A) is observed for a nominal P−C single bond with the tricoordinated phosphorus atom. The P−P distance (2.0750(18) A) in 12 is closer to the value for a PP bond than for a P−P bond. The sum of the bond angles at the tricoordinated phosphorus atom in 12 is 351.3°, making 12 the most planar 1H-[1,2]diphosphole known to date. The 31P NMR spectrum of 12 contains very similar chemical shifts for the tri- and dicoordinated phosphorus atoms (90.83 and 133.80 ppm), with a large P−P coupling constant (2JPP = 528.2 Hz). This is further evidence of significant delocalization of the lone pair electrons of the tricoordinated phosphorus into the ring system and is consistent ...
Databáze:	OpenAIRE
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