A polymeric phosphine sensor is reported that exhibits bright blue fluorescence in the presence of gold(I/III) ions but is nonemissive with other metal ions. Specifically, solutions of a poly(p-arylenediethynylene phosphine) copolymer are 35 or 94 times more emissive when treated with solutions of (tht)AuCl or HAuCl 4 •3H 2 O, respectively. Model compound studies confirm phosphine coordination to metals, including gold(I/III) and rhodium(I), and the selective "turn-on" fluorescence was investigated using time-dependent density functional theory calculations.

Phosphoranes P(OC6H4NR)2(OC6H4NHR) [R = Me (2a), Ph (2b), C6F5 (2c)] were synthesized by treating PCl5 with the respective 2-aminophenol derivative (1a-c, 3.1 equiv.). In one instance, an intermediate species, P(OC6H4NR)2Cl [R = Me (3a)], was isolated and structurally characterized. Deprotonation of the amine moieties (-NH[combining low line]R) in phosphoranes 2a and 2b with a strong alkali-metal base (e.g. n-BuLi) in the presence of a strong-donor solvent (e.g. THF) afforded salts composed of the hexacoordinate P(v)-anions [P(OC6H4NR)3]- (R = Me, [4a]-; Ph, [4b]-). Employing precursor 2a, the salt Li(THF)3fac-[4a]- was isolated. The X-ray crystal of each enantiomer of [4a]- was determined and, to our knowledge, represents the first structurally characterized example of a salt containing a hexacoordinate P(v)N3O3 anion featuring P(v)-N bonds.

The catalytic metathesis of C=C bonds is a textbook reaction that has no parallel in the widely studied area of multiple bonds involving heavier p-block elements. A high-yielding P=C bond metathesis of phosphaalkenes (ArP=CPh 2 , Ar = Mes, o-Tol, Ph) has been discovered that is catalyzed by N-heterocyclic carbenes (NHC = Me 2 IMe, Me 2 I i Pr). The products are cyclic oligomers formally derived from ArP=PAr [i. e. cyclo-(ArP) n ; n = 3, 4, 5, 6] and Ph 2 C=CPh 2 . Preliminary mechanistic studies of this remarkable transformation have established NHC=PAr (Ar = Mes, o-Tol, Ph) as key phosphinidene transfer agents. In addition, novel cyclic intermediates, such as, cyclo-(ArP) 2 CPh 2 and cyclo-(ArP) 4 CPh 2 have also been observed. This work represents a rare application of non-metal-based catalysts for transformations involving main-group elements.

The abnormal reaction of phosphaalkenes with N-heterocyclic carbenes (NHC) offers a convenient method to introduce new functionality at the backbone of an NHC. The 4-phosphino-substituted NHC (1a) derived from 1,3-dimesitylimidazol-2-ylidene (IMes) and MesP═CPh2 is shown to be an effective bifunctional ligand for Au(I) and Pd(II). Several new complexes are reported: 2a: 1a·AuCCl, 3a: 1a·(AuCl)2, 4a: [(1a)2AuC]Cl, 5a: [(1a·AuPCl)2AuC]Cl], and 6a: 1a·(PdC) (AuPCl). The reaction of 4-phosphino-NHC 1b, derived from 1,3-di(cyclohexyl)imidazol-2-ylidene (ICy) and MesP═C(4-C6H4F)2, with (tht)AuCl (2 equiv, tht = tetrahydrothiophene) affords the fascinating tetranuclear 5b [(1b·AuPCl)2AuC][AuCl2]. The molecular structure of 5b features a close Au···Au contact (3.0988(4) Å) between the bis(carbene)gold(I) cation and the dichloroaurate(I) anion. The buried volumes (%Vbur) and Tolman cone angles for representative 4-phosphino-NHCs calculated from structural data are compared to related carbenes and phosphines. The molecular structures are reported for complexes 3a, 4a, 5b, and 6a.