Surveying the {AuCl} adducts of bulky phosphines bearing the 2,6-dimesitylphenyl group

Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

“…At the outset of our work, however,j ust af ew terphenyl phosphine ligands, and ac onsequently small number of their complexesw ith late transition metals, had been described. [23][24][25] Our first reports centred on Rh, Ir,P ta nd Au complexes of PMe 2 Ar' phosphines (Ar' = C 6 H 3 -2,6-(C 6 H 3 -2,6-R 2 ) 2 forR = Me and iPr,i ns horthand notation PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 ,r espectively), and evinced their aptitude to stabilize low-coordinate structures, as well as their potentialt oadopt different coordination modes (Figure 1), where P-bondingi sc omplement-ed by relativelyw eak M···C arene interactions with af lanking aryl ring of the terphenyl substituent. [23][24][25][26][27][28] The objective of the present work was the description of a series of PR 2 Ar' molecules selected in accordance with the following criteria.…”

“…[23][24][25] Our first reports centred on Rh, Ir,P ta nd Au complexes of PMe 2 Ar' phosphines (Ar' = C 6 H 3 -2,6-(C 6 H 3 -2,6-R 2 ) 2 forR = Me and iPr,i ns horthand notation PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 ,r espectively), and evinced their aptitude to stabilize low-coordinate structures, as well as their potentialt oadopt different coordination modes (Figure 1), where P-bondingi sc omplement-ed by relativelyw eak M···C arene interactions with af lanking aryl ring of the terphenyl substituent. [23][24][25][26][27][28] The objective of the present work was the description of a series of PR 2 Ar' molecules selected in accordance with the following criteria. Firstly,b esides someP Me 2 -containing phosphines, [28,29] we set out to prepare PR 2 Ar' phosphines of the branched andc yclic alkyl groups iPr and c-C 6 H 11, respectively, which are phosphine substituents extensively employed in organometallic chemistry and catalysis.…”

“…Differentc oordination modes found for terphenyl phosphines. [23][24][25][26][27][28] analogous phosphine dicarbonyl Ni 0 compounds are unknown. Furthermore, we were surprised to learn that nearly fifty years after the generation by To lman of Ni(CO) 3 (PR 3 )c omplexes in CH 2 Cl 2 solutions, [35] there is an astonishing dearth of crystallographic information on compounds of this type.…”

P–P σ-bond activation by gold(I) coordination

“…26 In contrast, the terminal Au2-P2 distance in 5 (Figure 4) is considerably smaller and amounts to 2.2158(8) Å in accord with values known from terphenylphosphane complexes auf Au-Cl. 27 Interestingly, the Au-Cl unit is localized asymmetrically between the two P atoms with an almost linear P1-Au1-Cl1 moiety (4: 171.30(3)°, 5: 172.36(4)) leading to a "T-shaped" P1-Au-P2-Cl fragment with a rare pseudo-square planar coordination geometry. This rather awkward arrangement in AuCl adducts 4 and 5 is stabilized by η 3 coordination (Au···C 2.65 -3.2 Å, cf.…”

Terphenyl(bisamino)phosphines: Electron-rich Ligands for Gold-Catalysis

“…Upon coordi nation to AuCl the sum of angles at phosphorus increases [Σ(<P) (2a) 321.13°, (2b) 323.55°, cf. (TerPMe2)AuCl 318.33°] 29 In 2a and 2b there are close contacts between Au1 and one of the flanking terphenyl groups [(2a) C21-Au1 3.1008(43); (2b) C17-Au1 2.9707(20) Å], which is in contrast to the known complex (TerP Me2)AuCl. 29 This stabilizing arene-interaction was further authenticated through an analysis of the electron density of an optimized structure at the wB97XD/6-31g(d,p) level of theory, using the AIM (Atoms in Molecules) approach.…”