Synthesis and Structure of Cyanomethyltriphenylphosphonium Dicyanoaurate and Benzyltriphenylphosphonium Dicyanoargentate

Abstract

The interaction of potassium dicyanoaurate and dicyanoargentate with organyltriphenylphosphonium chlorides in water leads to complexes [PH3PH2CN]+[Au(CN)2]– (1) and [PH3PH2PH]+[Ag (CN)2] (2), which and structurally characterized. The phosphorus atoms in organyltriphenylphosphonium cations have a distorted tetrahedral coordination: the CPC angles equal 106.21(17)–111.02(16)° (1), 106.13(7)–111.06(7)° (2), The P-C bonds are 1.782(3)–1.818(3) Å (1) and 1.7985(16)–1.8064(16) Å (2). In the almost linear [Au(CN)2]− anions the CAuC angles are 178.10(19)° (1), the Au-C distances are 1.976(5) and 1.989(5) Å. Similar values in the [Ag(CN)2]– anions are equal to 178.29(8)° and 2.081(3), 2.089 (3) Å, respectively. According to the X-ray analysis performed at 293 K on an automatic four-circle diffractometer D8 Quest Bruker (two-coordinate CCD detector, MoK radiation,  = 0.71073 Å, graphite monochromator), crystals 1 (C22H17N3PAu, M 551.32, rhombic syngony P212121, crystal size 0.42×0.20×0.15 mm), cell parameters: a = 8.430(5), b = 13.696(6), c = 18.000(7) Å; α = 90.00 deg., β = 90.00 deg., γ = 90.00 deg.; V = 2078(4) Å3; the data collection area for 2 is 6.1–54.36 degrees, reflection index intervals –10 ≤ h ≤ 10, –17 ≤ k ≤ 17, –23 ≤ l ≤ 23; total re-flections 32161; independent reflections 4597; Rint = 0.0296; GOOF 1.133; R1 = 0.0241, wR2 = 0.0548; residual electron density 0.36/–1.59 e/Å3; crystals 2 (C27H22N2PAg, M 513.31, monoclin-ic syngony P21/s, crystal size 0.52×0.27×0.17 mm), cell parameters: a = 9.817(3), b = 15.131(6), c = 15.347(5) Å; α = 90.00 deg., β = 90.638(12) deg., γ = 90.00 deg.; V = 2279.6(14) Å3; the data collection area for 2 is 6.7–72.86 degrees, the reflection index intervals are –16 ≤ h ≤ 16, –25 ≤ k ≤ 25, –25 ≤ l ≤ 25; total reflections 67366; independent reflections 11062; Rint = 0.0316; GOOF 1.031; R1 = 0.0403, wR2 = 0.0925; residual electron density is 0.38/–0.74 e/Å3.