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“…The outcome of the three-component reactions of the 2Hazaphosphirene complexes 1 a, 1 b, [11] and 1 c [12] with two equivalents of 1-piperidinonitrile and TCNE in toluene at 75 8C was surprising and depended significantly on the metal; complexes 1 a, b yielded no reaction products that could be identified or isolated. In the case of the tungsten complex 1 c, the D 5 -1,2-azaphospholene complex 2 c, a non-identified byproduct (d 163.9; < 5 %) and the 2H-1,4,2-diazaphosphole complex 3 c (< 5 %) were formed (Scheme 2); the reaction to WILEY-VCH Verlag GmbH, D- form 2 c represents the first example of a 1,3-dipolar cycloaddition of a nitrilium phosphane ylide complex to an alkene derivative.…”

Li/X Phosphinidenoid Pentacarbonylmetal Complexes: A Combined Experimental and Theoretical Study on Structures and Spectroscopic Properties

“…As previously demonstrated halogeno(organo)phosphane complexes enable access to Li/X phosphinidenoid complexes via P -H deprotonation − Therefore, we first synthesized complexes 3a , 3b,c (X = Cl), 4 (X = Br), and 5 (X = I) using a selective thermal ring-cleavage reaction of 2 H -azaphosphirene complexes 1a – c in the presence of triethylammonium halides (Scheme ). Complex 5 was prepared using in situ formed [Et 3 NH]I, obtained under typical 2 H -azaphosphirene complex synthesis conditions while employing [bis(trimethylsilyl)-methylene]iodophosphaneand the appropriate aminocarbene complex, and heating of the resulting reaction solution.…”

Deoxygenation of carbon dioxide by electrophilic terminal phosphinidene complexes

“…Transient electrophilic terminal phosphinidene complexes 2a,b, generated by thermolysis of 2H-azaphosphirene complexes 1a,b, 32,33 react at 75 C with carbon dioxide (50 bar) to yield selectively cis and trans 1,3-dioxa-2,4-diphosphetane complexes 5a,b and 6a,b which were isolated and unambiguously characterised (Scheme 2). 34 The deoxygenation of CO 2 by terminal phosphinidene complexes 35 2a,b is assumed to proceed via intermediate oxaphosphiranone complexes 3a,b (i), which subsequently extrude CO to form phosphinidene oxide complexes 4a,b (ii).…”