Reactions of Potassium Bis(phosphinimino)methanide with Group 11 Compounds

Abstract

Transmetalation of the potassium methanide complex, K{CH(PPh2NSiMe3)2}, with [(Ph3P)2CuI] afforded the corresponding copper complex [{CH(PPh2NSiMe3)2}CuPPh3] (1), whereas the reaction of K{CH(PPh2NSiMe3)2} with [Ph3PAuCl] resulted in the dinuclear gold complex [(Ph3PAu)2{C(PPh2NSiMe3)2}] (2). The solid-state structure of 1 shows the formation of a six-membered metallacycle (N1-P1-C1-P2-N2-Cu) that has a twist boat conformation. In contrast, compound 2 is an alpha,alpha-diaurated species, in which the two gold atoms are coordinated in a linear fashion onto the ligand backbone. Photoluminescence measurements show that the latter compound has a strong violet emission.

Synthesis and Structural Characterization of Mono‐ and Bimetallic Rhodium(I), Iridium(I) and Gold(I) Methanide and Methandiide Complexes from 2‐Quinolyl‐Linked (Thiophosphoranyl)methane

“…In addition, the gold atoms do not coordinate to any S or N donor atoms from the ligand. The average Au–C methandiide bond length of 2.13 Å is in good agreement with those values found in [(Ph 3 PAu) 2 {C(PPh 2 NSiMe 3 ) 2 }] (average Au–C = 2.102 Å) . The average Au–P triphenylphosphine bond length of 2.268 Å is also comparable to that found in [(Ph 3 PAu) 2 {C(PPh 2 NSiMe 3 ) 2 }] [average Au–P = 2.266 Å] .…”

“…Furthermore, the gold atom does not coordinate to any S or N donor atoms from the ligand. The Au–C methanide bond length of 2.098(6) Å is comparable to that found in 6 and shows good agreement with those found in [(Ph 3 PAu) 2 {C(PPh 2 NSiMe 3 ) 2 }] (average Au–C = 2.102 Å) …”

“…of AuCl(PPh 3 ) affords the dinuclear gold(I) methandiide complex. A similar diaurated complex has been reported by Roesky et al, and is supported by the ligand derived from bis(iminophosphoranyl)methane . Attempts to prepare the copper complex by reacting 1 with [CuCl(PPh 3 )] were not successful; only unreacted 1 was obtained.…”

“…The UV/Vi absorption spectra of compounds 2 – 6 were obtained and the results are shown in Table S3 (see the Supporting information). Absorption peaks beyond 380 nm are assignable to ligand‐to‐metal charge transfer (LMCT) interactions . The presence of an additional metal center in 4 and 5 causes a redshift in the absorption peaks.…”

(Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis

“…Both ligands have been extensively used in main group, 1-16 transition [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] and f-element 5,13,15,19,[35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] chemistry. Both ligands have been extensively used in main group, 1-16 transition [16][17][18][19][20][21][22][23][24][25][26][27][28][29]…”