Structural features of di(1-adamantyl)benzylphosphane complexes of Cu(I) and Ag(I)

First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

“…In 3 the P1–Cu1–P3 angle is approximately linear (177.23(7)°) and is comparable to other complexes with CuP 2 core: [Li(thf) 2 ][Cu(P t Bu 2 ) 2 ] (176.5(6)°)[1c] and [Cu(PCy 3 ) 2 ][PF 6 ] (179.47(3)°) . The Cu–P distances in 3 (2.2080(13) Å and 2.2098(12) Å) are analogous to these found in complexes [Cu(PBz 3 ) 2 ][PF 6 ] (2.191(1) Å) and [Cu(PCy 3 ) 2 ][PF 6 ] (2.213 (4) Å), but slightly shorter that these occurring in complexes [Cu(PAdm 2 Bz) 2 ][BF 4 ] · 2CHCl 3 (2.228(2) Å, 2.239(3) Å) and [Li(thf) 2 ][Cu(P t Bu 2 ) 2 ] (2.246(5) Å and 2.266(4) Å). [1c] On the other hand, the P–P distances (2.1864(17) Å, 2.1953(17) Å) are much shorter than these in complex 1 , but they are still within the range of single P–P bond.…”

Structural trends in a series of bulky dialkylbiarylphosphane complexes of CuI

“…The P-Cu-X angles are much smaller in 6 compared to complexes 1-5, which can be attributed to the different coordination sphere. The Cu-P bond lengths are also longer than in the other complexes, but are within the range of similar three-coordinate Cu I complexes, as are the Cu-N and Cu-S bond lengths (Bowmaker et al, 2012;Davidson et al, 2016;Dodds & Kennedy, 2014;Dodds et al, 2019;Romanov et al, 2017;Wilk et al, 1992). Each Cu I centre lies slightly outside the plane of the donor set (0.17-0.21 Å ), which was not observed in the previously reported tri-tert-butylphosphane and bis(adamantan-1-yl)benzylphosphane analogues (Bowmaker et al, 2012;Davidson et al, 2016).…”

“…The Cu-P bond lengths are also longer than in the other complexes, but are within the range of similar three-coordinate Cu I complexes, as are the Cu-N and Cu-S bond lengths (Bowmaker et al, 2012;Davidson et al, 2016;Dodds & Kennedy, 2014;Dodds et al, 2019;Romanov et al, 2017;Wilk et al, 1992). Each Cu I centre lies slightly outside the plane of the donor set (0.17-0.21 Å ), which was not observed in the previously reported tri-tert-butylphosphane and bis(adamantan-1-yl)benzylphosphane analogues (Bowmaker et al, 2012;Davidson et al, 2016). Based on the distance between the Cu I centre and the plane of the arene ring, the Cu I -arene interactions in 6 are not significant (3.05-3.06 Å ), likely due to Cu I having sufficient electron density from the three coordinated ligands.…”

“…The bulkiness of two tribenzylphosphane sulfide ligands in the related [Cu(MeCN)(SPBn 3 ) 2 ]PF 6 complex prevented the coordination of a third phosphane sulfide . The bis(adamantan-1-yl)benzylphosphane ligand gave a two-coordinate complex with a slightly bent geometry due to the influence of the adamantyl groups (Davidson et al, 2016). This article investigates a series of Cu I complexes, 1-6 (see Scheme 1), containing t BuXPhos and a simple monoanionic or neutral ligand.…”

Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

“…The crystal structure depicted in Fig. 5 reveals a bent P1-Cu1-P2 geometry (1641), 25 which is usually observed with very bulky ligands 26 and reflects the high steric demand of ligand 9. The Cu-P distances are comparable with those of similar complexes.…”