Darstellung und Kristallstrukturen von Dicyanamido(triphenylphosphan)gold(I) und Nitrosodicyanmethanido(triphenylphosphan)gold(I)

Abstract

Professor Josef Goubeau in memoriamInhaltsu È bersicht. Die Koordinationsverbindungen [(Ph 3 P)-Au{N(CN) 2 }] (1) und [(Ph 3 P)Au{ONC(CN) 2 }] (2) werden durch Umsetzung von [Au(PPh 3 )]NO 3 mit Na[N(CN) 2 ] bzw. K[ONC(CN) 2 ] in CH 2 Cl 2 erhalten. Die Verbindungen werden IR-spektroskopisch und durch Kristallstrukturanalysen charakterisiert. 1 kristallisiert triklin in der Raumgruppe P 1 mit a = 930,16(4), b = 1011,89(13), c = 1118,35(16) pm, a = 115,327(10), b = 90,899(8), c = 103,394(8)°, Z = 2. 2 kristallisiert monoklin in der Raumgruppe P2 1 /n mit a = 832,59(10), b = 1139,30(16), c = 2078,9(4) pm, a = 99,84(2)°, Z = 4. Die Kristallstrukturen beider Verbindungen sind aus paarweise antiparallel angeordneten Moleku È len mit linear koordinierten Goldatomen und schwachen zwischenmolekularen Au±N-Wechselwirkungen aufgebaut. Preparation and Crystal Structures of Dicyanamido(triphenylphosphane)gold(I) and Nitrosodicyanomethanido(triphenylphosphane)gold(I) Abstract. The coordination compounds [(Ph 3 P)Au{N(CN) 2 }] (1) and [(Ph 3 P)Au{ONC(CN) 2 }] (2) are obtained by the reaction of [Au(PPh 3 )]NO 3 with Na[N(CN) 2 ] or K[ONC(CN) 2 ] in CH 2 Cl 2 . The compounds are characterized by IR spectroscopy and by crystal structure determination. 1 crystallizes triclinic in the space group P 1 with a = 930.16(4), b = 1011.89(13), c = 1118.35(16) pm, a = 115.327(10), b = 90.899(8), c = 103.394(8)°, Z = 2. 2 crystallizes monoclinic in the space group P2 1 /n with a = 832.59(10), b = 1139.30(16), c = 2078.9(4) pm, b = 99.84(2)°, Z = 4. The crystal structures of both compounds are built up by pairs of antiparallel oriented molecules with linear coordinated gold atoms and weak intermolecular Au±N-interactions.

Low-dimensional compounds containing cyano groups. XV. Preparation, crystal structure and spectral properties of three copper(II) nitrosodicyanomethanide complexes

“…It coordinates to the central atom mostly as a terminal O-bonded ligand [2], but several compounds with a terminal N-bonded ndcm were reported, too [3]. O-coordination of ndcm was also observed in the [Cu(bipy)(mcoe){ONC(CN) 2 }] compound in which another anionic ligand, mcoe = methyl(2-cyano-2-imidoxy ethaneimidate), [(ON)(NC)C-C(NH)(OCH 3 )] -, is present [4].…”

“…In our previous work, we have studied structures of fivecoordinate copper(II) complexes of a general formula [Cu(L) 2 X]C(CN) 3 , where L is phen or bipy and X is an N-donor pseudohalide anion. Although we could prepare series of compounds with L = bipy and X = CN -, NCO -, NCS -, N(CN) 2 -and C(CN) 3 -, and L = phen and X = CN -, NCS -and N(CN) 2 - [9], we have not succeeded in preparing a homologous compound with X = ONC(CN) 2 -.…”

“…Although we could prepare series of compounds with L = bipy and X = CN -, NCO -, NCS -, N(CN) 2 -and C(CN) 3 -, and L = phen and X = CN -, NCS -and N(CN) 2 - [9], we have not succeeded in preparing a homologous compound with X = ONC(CN) 2 -. Our attempts to prepare this desired compound resulted in [Cu(bipy)(coe)], where coe = 2-cyano-2-imidoxy ethaneimidate, [(ON)(NC)C-C(NH)(O)] 2- [10], which is formed by nucleophilic addition of a hydroxide ion to the coordinatively activated b-carbon atom of ndcm.…”

“…Our attempts to prepare this desired compound resulted in [Cu(bipy)(coe)], where coe = 2-cyano-2-imidoxy ethaneimidate, [(ON)(NC)C-C(NH)(O)] 2- [10], which is formed by nucleophilic addition of a hydroxide ion to the coordinatively activated b-carbon atom of ndcm. We decided to replace C(CN) 3 -by other -1 anions (Y) in an effort to prepare complexes of the type [Cu(L) 2 …”

“…Preparation of the title complexCrystals of (1b) were prepared by mixing an aqueous solution of Cu(CF3 SO 3 ) 2 (0.1 M, 5 cm 3 ) with a methanol solution of bipy (0.1 M, 10 cm 3 ) and a methanol solution of NaONC(CN) 2 (0.1 M, 5 cm 3 ). The mixture of dark green crystals of (1b) and light-green crystals, probably of [Cu(bipy) 3 ][Cu(bipy) 2 {ONC(CN) 2 }](CF 3 SO 3 ) 3 composition, appeared after a few days.…”