Gold(I)‐Komplexe eines geminalen Bis(phosphino)allens

Abstract

1,1‐Bis(diphenylphosphino)‐3‐methyl‐1,2‐butadien (1) kann mit einem oder zwei Äquivalenten Carbonyl(chloro)gold(I) unter CO‐Entwicklung zu den entsprechenden 1:1‐ und 1:2‐Komplexen (2, 3) umgesetzt werden. Die Kristallstrukturuntersuchung am 1:1‐Komplex weist das Vorliegen von zwei kristallographisch unabhängigen, zentrosymmetrischen Dimeren nach, in denen die beiden Goldatome einen transannularen Abstand von 3.070(1) bzw. 3.002(1) Å haben. Die Chloratome sind so gebunden, daß an den Goldatomen eine T‐förmige Koordinationsgeometrie entsteht.

Coordination Chemistry of the cyclo‐(P5tBu4)− Ion: Monomeric and Oligomeric Copper(I), Silver(I) and Gold(I) Complexes

“…The gold atom shows an almost linear geometry (P1 À Au1 À P6 172.91(4)8) with bond lengths in the range of other Au I phosphanido and phosphane complexes (Au1 À P1 233.3(2), Au1 À P6 230.1(2) pm). [13,21,22] The (6) pm) are similar to those reported for other Cu I [11,12] and Ag I [12] phosphanido complexes, respec-tively. The P À M À P angles deviate slightly from linearity (162.69 (5) [20] Packing diagrams of the molecular structures of 5 and 6 illustrate the presence of n-hexane solvent molecules in pockets formed by four molecules of 5 or 6 ( Figure 6).…”

“…The Au À P bond lengths in 9 (231.6(3), 232.1(3) pm) are similar to those in other Au I complexes. [13,21,22] The slightly bent coordination of the two-coordinate gold atoms (P1ÀAu1ÀP1A 167.0(2)8) is comparable to that of the related gold(I) phosphanido complex [{Au-A C H T U N G T R E N N U N G (PMes 2 )} 4 ]. [13] The P À P bond lengths are typical for single bonds.…”

“…[13] The P À P bond lengths are typical for single bonds. [20] Gold(I) complexes often exhibit inter-or intramolecular Au À Au contacts ( % 300 pm), [21,22] but the corresponding Au···Au distances in tetranuclear gold complex 9 are much longer ( % 510.5 pm).…”

The fascinating implications of new results in gold chemistry

“…It is thus only the evaluation of the complete three-dimensional system which tells the true story. To illustrate this point, the formulae in Figure 7 can be used to systematize, for example, the complexes of AuCl with difunctional phosphines showing major or only subtle differences in-their basic skeleton [47][48][49][50][51][52]. Again, the differences as compared to related silver complexes should be noted [53].…”

“…The most common chair conformation and the (less well represented undistorted) boat conformation have two X-Au-Y axes (X,Y = ligand donor element) running parallel to each other, while in the twist conformation these axes form small angles, but with the line connecting the two gold atom as their closest approach [58][59][60][61][62][63][64][65]. The `elongated cyclohexane' structure is found with di-phosphinomethanes, phosphonium bis(methylides) (`glides'), di-thio-phosphates and di-thio-phosphinates or -phosphonates [13], and even inorganic ligands like tetra-thiotungstate, WS42- [66], or tetrathiostannate SnS44- [67].…”