Monometallic Ni0 and Heterobimetallic Ni0/AuI Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis

The tridentate chelate nickel complexes [(CO)Ni{(PPh₂CH₂)₃CMe}] ( 2 ), [(CO)Ni{(PPh₂CH₂CH₂)₃SiMe}] ( 6 ), and [Ph₃PNi{(PPh₂CH₂CH₂)₃SiMe}] ( 7 ), as well as the bidentate complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂PPh₂}] ( 3 ) and the heterobimetallic complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂Ph₂PAuCl}] ( 4 ), have been synthesized and fully characterized in solution. All ¹H and ¹³C NMR signal assignments are based on 2D‐NMR methods. Single crystal X‐ray structures have been obtained for all complexes. Their ³¹P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2 – 4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction.     

Preparation and Characterization of a Novel Palladium Complex: cis‐Dichloride(1,2‐bis(diphenylphosphino)vinyl‐P,P′,C)palladium(II)‐(bis(diphenylphosphino)methane‐P,P′)cobaltacarbonyl

A novel palladium complex 4, cis‐dichloride(1,2‐bis(diphenylphosphino)vinyl‐P,P′,C)palladium(II)‐(bis(diphenylphosphino)methane‐P,P′)cobaltacarbonyl, was obtained and characterized from the treatment of [(μ‐Ph₂PCH₂PPh₂)Co₂(CO)₄][(Ph₂PC≡CPPh₂)‐PdCl₂] 3 with hydrochloric acid. The framework of 4 can be regarded as a grouping of two metal‐containing fragments: ‐Co(CO)₂(dppm) and PdCl2(μ‐P,P‐Ph₂PCH=C(‐)PPh₂).     

Gallium(III) halide complexes with phosphines,arsines and phosphine oxides – a comparative study

The phosphine oxide complexes [GaX₃(Me₃PO)] and [(GaX₃)₂{μ-o-C₆H₄(CH₂P(O)Ph₂)₂}] have been prepared and characterised by microanalysis, IR and multinuclear NMR (¹H, ¹³C{¹H}, ³¹P{¹H} and ⁷¹Ga) spectroscopy. The structures of [GaCl₃(Me₃PO)], [(GaBr₃)₂{μ-o-C₆H₄(CH₂P(O)Ph₂)₂}] and of the ionic product [GaI₂(Me₃PO)₂][GaI₄] have been determined and show that the Lewis acidity of the gallium halides towards phosphinoyl ligands diminishes as the halogen becomes heavier. The [GaX₃(Ph₃E)] (X = Cl, Br or I; E = P or As) and [(GaX₃)₂{μ-o-C₆H₄(CH₂PPh₂)₂}] (X = Br or I) have been prepared and their structural and spectroscopic properties compared with those of the phosphinoyl complexes. The results, and competitive solution NMR studies, show that Ga(III) binds the hard R₃PO in preference to the softer phosphine or arsine ligands. Hydrolysis of gallium(III) phosphines is shown to lead to [R₃PH][GaX₄], but in contrast to some other p-block halides, GaX₃ do not promote air-oxidation of R₃P to R₃PO.     

Chemie polyfunktioneller Moleküle. 82. Neue Rhodium(I)-Chelatkomplexe mit N,N-Bis(diphenylphosphino)alkyl- und -arylaminen

Chemistry of Polyfunctional Molecules. 82. New Rhodium(1) Chelate Complexes with N,N-Bis(diphenylphosphino) alkyl- and -arylamines . [Rh(μ-Cl)(CO)₂]₂ ( 1 ) reacts with (Ph₂P)₂NR (2, a: R = C₆H₅, b: R = p-C₆H₄CH₃) in a molar ratio of 1:2 to give the square plane, ionic complexes [Rh{(PH₂P)₂NR}₂] [cis-Rh(CO)₂Cl₂] ( 3a, b ). By the reactions of [Rh(μ-Cl)(C₈H₁₂)]₂(C₈H₁₂ = 1.5-Cyclooctadiene) (4) with (Ph₂P)₂NR ( 2a–d ) (c: R = CH₃, d: R = C₂H₅) in the molar ratios of 1:4 the square plane 1:1 electrolytes [Rh{(Ph₂P)₂NR}₂]Cl ( 5a–d ) are obtained. Upon treatment of 5a–d in dichloromethane with CO the complexes [Rh(CO){(Ph₂P)₂NR}₂]Cl ( 6a–d ) are formed. They are only stable in solution and in CO atmosphere and were identified by infrared spectroscopy. The new complexes have been characterized, as far as possible, by conductometry, IR; FIR, Raman, ³¹P-NMR, and ¹H-NMR spectra.     

Hydrophilic Quaternary Ammonium‐Group‐Containing [FeFe]‐Hydrogenase Models: Synthesis,Structures, and Electrocatalytic Hydrogen Production

The first quaternary ammonium‐group‐containing [FeFe]‐hydrogenase models [(μ‐PDT)Fe₂(CO)₄{κ²‐(Ph₂P)₂N(CH₂)₂NMe₂BzBr}] ( 2 ; PDT=propanedithiolate) and [(μ‐PDT)Fe₂(CO)₄{μ‐(Ph₂P)₂N(CH₂)₂NMe₂BzBr}] ( 4 ) have been prepared by the quaternization of their precursors [(μ‐PDT)Fe₂(CO)₄{κ²‐(Ph₂P)₂N(CH₂)₂NMe₂}] ( 1 ) and [(μ‐PDT)Fe₂(CO)₄{μ‐(Ph₂P)₂N(CH₂)₂NMe₂}] ( 3 ) with benzyl bromide in high yields. Although new complexes 1 – 4 have been fully characterized by spectroscopic and X‐ray crystallographic studies, the chelated complexes 1 and 2 converted into their bridged isomers 3 and 4 at higher temperatures, thus demonstrating that these bridged isomers are thermodynamically favorable. An electrochemical study on hydrophilic models 2 and 4 in MeCN and MeCN/H₂O as solvents indicates that the reduction potentials are shifted to less‐negative potentials as the water content increases. This outcome implies that both 2 and 4 are more easily reduced in the mixed MeCN/H₂O solvent than in MeCN. In addition, hydrophilic models 2 and 4 act as electrocatalysts and achieve higher i_cat/i_p values and turnover numbers (TONs) in MeCN/H₂O as a solvent than in MeCN for the production of hydrogen from the weak acid HOAc.     

Tellurium(II) and tellurium(IV) complexes of phosphine chalcogenide ligands,synthesis and X-ray structures

Reaction of TeX₄ (X = Cl or Br) with 2 mol. equiv. of OPR₃ (R = Me, Et or Ph) gives the distorted octahedral cis-[TeX₄(OPR₃)₂], while the bidentates Ph₂P(E)(CH₂)_nP(E)Ph₂ (E = O, n = 1 or 2; E = S, n = 1) give the six-coordinate [TeX₄{Ph₂P(E)(CH₂)_nP(E)Ph₂}]. These species have been characterised spectroscopically (via ¹H and ³¹P{¹H} NMR and IR) and by crystallographic analyses on cis-[TeBr₄(OPPh₃)₂], [TeCl₄{Ph₂P(O)CH₂P(O)Ph₂}] and [TeBr₄{Ph₂P(S)CH₂P(S)Ph₂}]. The TeX₄ (X = Cl or Br) are reduced by Ph₂P(S)(CH₂)₂P(S)Ph₂ and Ph₂P(Se)CH₂P(Se)Ph₂, giving the planar, four-coordinate Te(II) species [Te{Ph₂P(S)(CH₂)₂P(S)Ph₂}₂]²⁺ (isolated as [(TeCl₅)₂{μ-Ph₂P(S)(CH₂)₂P(S)Ph₂}]^2? and [TeBr₆]^2? salts) and [TeBr₂{Ph₂P(Se)CH₂P(Se)Ph₂}], all of which have also been identified crystallographically. On the basis of the structural data the Te-based lone pair associated with the Te(IV) species is assumed to occupy the 5s orbital, whereas in the Te(II) complexes the planar coordination is consistent with the two stereochemically active lone pairs occupying the axial sites.     

Conjugate additions of functionalized carbanions to the vinylidene groups of [M(CO)4{(Ph2P)2CCH2}] (M = W,Mo or Cr)

Treatment of complexes of the type [M(CO)₄{(Ph₂P)₂CCH₂}] (M = W, Mo or Cr) with functionalized lithium reagents, LiR, followed by hydrolysis gives complexes of the type [M(CO)₄{PH₂P)₂CHCH₂R}] in high yields; R = C₆H₄Me-4, C₆H₄OMe-2, C₆H₃(OMe)₂-2,6, C₆H₄OH-2, C₆H₄(COOH)-2, CH₂COPh or CH₂COMe. IR, and ³¹P and ¹H NMR data are given.     

Crystal and molecular structures of some six‐coordinate tin(IV) halogeno complexes with phosphorus‐containing ligands

Six new complexes of tin(IV) halides with phosphorus‐containing ligands have been fully characterized by single‐crystal X‐ray diffraction at low temperature. Three of the compounds, derived from the diphosphanes bis‐(diphenylphosphino)methane or bis‐(dicyclohexylphosphino)methane, have a novel zwitterionic structure, with five Cl ligands and one unidentate phosphorus‐containing ligand on tin, together with a proton on the second phosphorus atom of the potentially bidentate ligand; these are Cl₅Sn⁻P(Ph₂)CH₂PPh₂H⁺ ( 1 ), Cl₅Sn⁻OP(Ph₂)CH₂‐PPh₂H⁺ ( 2 ), and Cl₅Sn⁻OP(cy₂)CH₂Pcy₂H⁺ ( 3 ). The other three complexes have a bidentate donor attached to the SnX₄ moiety; they comprise Cl₄SnOP(Ph₂)‐(CH₂)₂PPh₂O ( 4 ), a derivative of bis‐(diphenylphosphino)ethane dioxide, I₄SnOP(Ph₂)CH₂PPh₂O ( 5 ), a similar derivative of bis‐(diphenylphosphino)‐methane dioxide, and the very unusual Br₄SnAs‐(Ph₂)(CH₂)₂PPh₂O ( 6 ), with coordination to tin by As and O. Since the starting material for the last compound was Ph₂As(CH₂)₂PPh₂, this result illustrates well the more facile oxidation of P(III) than As(III). © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:136–143, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20525     

Clusteraufbau durch Photolyse von R3PAuN3. VIII. Synthese und Kristallstruktur von [(Ph3PAu)5Mo(CO)4]PF6 · CH2Cl2 und (Ph3PAu)3Co(CO)3

Cluster Synthesis by Photolysis of R₃PAuN₃. VIII. Synthesis and Crystal Structure of [(Ph₃PAu)₅Mo(CO)₄]PF₆ · CH₂Cl₂ and (Ph₃PAu)₃Co(CO)₃ Photolysis of a mixture of Ph₂PAuN₃ and Mo(CO)₆ in THF yields [(Ph₃PAu)₅Mo(CO)₄]⁺ (1), which can be crystallized from CH₂Cl₂/diisopropylether as orange 1 · PF₆ · CH₂Cl₂ with the space group P2₁/c and a = 1681.4(5), b = 2215.6(12), c = 2761.5(9) pm, β = 91.54(3)°, Z = 4. The Au₅Mo center of cluster 1 forms a capped trigonal bipyramid with the Mo atom in equatorial position and almost equal Mo? Au distances between 279.9(5) and 284.6(7) pm to all five Au atoms. The Au? Au distances range from 272.2(4) to 301.3(4) pm. The Mo(CO)₄ group causes three v(C0) at 1975, 1915 and 1890cm^?1. Reaction of Ph₃PAuCo(CO)₄ with Ph₃PAuPF₆ affords the known cluster cation [(Ph₃PAu)₄Co(CO)₃]⁺ in high yield. It can be degraded with C1^? to the neutral cluster (Ph₃PAu)₃Co(CO)₃ (2). 2 forms air stable, yellow crystals with the space group P2₁/n and a = 1359.4(4), b = 2041.0(5), c = 1853.2(6)pm, β = 91.47(1)°, Z = 4. The Au₃Co core of 2 has a tetrahedral structure with distances Co? Au between 250.4(1) and 254.0(2) pm and Au? Au between 279.5(1) and 285.1(1) pm. v(C0) are observed at 1963, 1905 and 1891 cm^?1. Reaction of 2 with [(Ph₃PAu)₄Co(CO)₃]⁺ yields the condensed cluster [(Ph₃PAu)₆AuCo₂(CO)₆]⁺.     

Dinuclear group VIB metal carbonyl complexes bridged by bis(diphenylphosphino)alkanes

Reactions of the intermediate W(CO)₅THF, generated photochemically from W(CO)₆ in THF, with Ph₂P(CH₂) _n PPh₂ [ = PP; n = 2 (dppe), 4 (dppb), 6 (dpph), 10 (dppd)] at room temperature in THF solutions gave exclusively bimetallic complexes of the (CO)₅WPPW(CO)₅ type. In addition, complexes bridged by diphosphine ligands of the (CO)₄(pip)MPPM(pip)(CO)₄ type (pip = piperidine; M = Mo, W) were prepared by stirring the (CO)₄M(pip)₂ complexes with bis(diphenylphosphino)alkanes in CH₂Cl₂ solution at ambient temperatures. These new bis(diphenylphosphino)alkane-bridged complexes were characterized by i.r., ¹H- and ³¹P-n.m.r. spectroscopies, as well as by elemental analysis.     

Olefin isomerisation by group via metals

2-(MeR¹CCR²)-and 2-(CH₂CR¹CH₂CH₂)-pyridine (R¹,R² = H or Me) undergo 1,2-double-bond shifts and 2-(CH₂CHCH₂CH₂CH₂)-pyridine undergoes a 1,3-double-bond shift on displacement of norbornadiene from [M(CO)₄norb] (M = Cr, Mo or W) to give complexes of the type [M(CO)₄LL'] (LL' = 2-(allyl)or 2-(substituted allyl)-pyridine), which do not exhibit conformational isomerism involving the plane of the coordinated olefin.     

Photochemical reactions of Re(CO)5Br with Ph2P(CH2) n PPh2 (n = 1, dppm; 2, dppe; 3, dppp)

The new complexes fac-[Re(CO)₃Br{Ph₂P(CH₂) _n PPh₂}] (1a–3a) [(1a), n = 1; (2a), n = 2; (3a), n = 3] and [Re₂(CO)₈Br₂{-Ph₂P(CH₂) _n PPh₂}] (1b–3b) [(1b), n = 1; (2b), n = 2; (3b), n = 3] have been prepared by the photochemical reaction of Re(CO)₅Br with Ph₂P(CH₂) _n PPh₂ (n = 1, dppm; 2, dppe; 3, dppp). The complexes have been characterized by elemental analysis, mass spectroscopy, f.t.-i.r. and ³¹P-[¹H]-n.m.r. spectrometry. The spectroscopic studies suggest cis-chelate bidentate coordination of the ligand in fac-[Re(CO)₃Br{Ph₂P(CH₂) _n PPh₂}] (1a–3a) and cis-bridging bidentate coordination of the ligand between two metals in [Re₂(CO)₈Br₂{cis--Ph₂P(CH₂) _n PPh₂}] (1a–3a).     

The dimerization of diphenyl(cyclopentadienyl)phosphine ligands by Diels-Alder addition

Reaction of diphenyl(cyclopentadienyl)phosphine, 1, with [PdCl₂(PhCN)₂], [PtCl₂(SMe₂)₂] or [M(CO)₄(norbornadiene)], where M = Mo or W, gave the complexes [PdCl₂{(Ph₂P)₂C₁₀H₁₀}], [PtCl₂{(Ph₂P)₂C₁₀H₁₀}] or [M(CO)₄{(Ph₂P)₂C₁₀H₁₀}] respectively, in which the ligand underwent dimerization by Diels-Alder addition. The reaction occurs in a very selective way and this is rationalized in terms of a template effect, in which two ligands 1 in mutually cis positions undergo the Diels-Alder reaction. In contrast, the complex [Fe(CO)₄(Ph₂PC₅H₅)] is stable to Diels-Alder addition. The structures of the complexes were deduced by ¹H, ¹³C and ³¹P NMR spectroscopy. The major product contains a six-membered chelate ring while a minor product, formed in the palladium and platinum systems only, contains a five-membered chelate ring.     

Preparation and Reactivity of Mixed‐Ligands Hydride Complexes [RuHCl(CO)(PPh3)2{P(OR)3}]

Mixed‐ligands hydride complexes [RuHCl(CO)(PPh₃)₂{P(OR)₃}] ( 2 ) (R = Me, Et) were prepared by allowing [RuHCl(CO)(PPh₃)₃] ( 1 ) to react with an excess of phosphites P(OR)₃ in refluxing benzene. Treatment of hydrides 2 first with triflic acid and next with an excess of hydrazine afforded hydrazine complexes [RuCl(CO)(κ¹‐NH₂NHR1)(PPh₃)₂{P(OR)₃}]BPh₄ ( 3 , 4 ) (R1 = H, CH₃). Diethylcyanamide derivatives [RuCl(CO)(N≡CNEt₂)(PPh₃)₂{P(OR)₃}]BPh₄ ( 5 ) were also prepared by reacting 2 first with HOTf and then with N≡CNEt₂. The complexes were characterized spectroscopically and by X‐ray crystal structure determination of [RuHCl(CO)(PPh₃)₂{P(OEt)₃}] ( 2b ).     

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph₂P‐N‐PPh₂ at Group 4 metallocenes is presented herein. Coordination of N,N‐bis(diphenylphosphino)amine ( 1 ) to [(Cp₂TiCl)₂] (Cp=η⁵‐cyclopentadienyl) generated [Cp₂Ti(Cl)P(Ph₂)N(H)PPh₂] ( 2 ). The heterometallacyclic complex [Cp₂Ti(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Ti ) can be prepared by reaction of 2 with n‐butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp₂Ti(η²‐Me₃SiC₂SiMe₃)] with the amine 1 . Reactions of the lithium amide [(thf)₃Li{N(PPh₂)₂}] with [Cp₂MCl₂] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp₂M(Cl){κ²‐N,P‐N(PPh₂)₂}] ( 4 Zr and 4 Hf ). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp₂Zr(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Zr ). Complexes 2 , 3 Ti , 4 Hf , and 3 Zr were characterized by X‐ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations.     

Functionalised Tris(pyrazolyl)methane Ligands and Re(CO)3 Complexes Thereof

The synthesis of new tripodal nitrogen ligands derived from tris(pyrazolyl)methane (Tpm^R, R = H, tBu, Ph in 3‐position) is described. After deprotonation of the parent tris(pyrazolyl)methane Tpm^R, the carbanion reacts readily with ethylene oxide to yield the 3,3,3‐tris(3′‐substituted pyrazolyl)propanol ligands[(3‐Rpz)₃CCH₂CH₂OH, R = H, tBu, Ph, 1a – c ]. These ligands can be easily derivatised at the alcohol function. Microwave‐assisted reactions of these ligands and [Re(CO)₅Br] yields the complex [( 1a )Re(CO)₃]Br ( 4 ) in the case of ligand 1a , whereas in the case of the substituted ligands 1b and 1c degradation was observed. The degradation products are identified as [(Hpz^R)₂Re(CO)₃Br] [R = tBu ( 7b ), Ph ( 7c )]. These complexes were also prepared directly from [Re(CO)₅Br] and the corresponding pyrazoles by microwave‐assisted synthesis. The Re(CO)₃ complexes 4 and [( 1a )Re(CO)₃]OTf ( 5 ) are water‐soluble. The structures of 5· H₂O and [{(pz)₃CCH₂CH₃}Re(CO)₃]OTf · 1.5H₂O · ¹/₂CH₃CN ( 6· 1.5H₂O · ¹/₂CH₃CN) as well as the structure of 7b have been elucidated by X‐ray crystallography.     

Molybdenum(0) and Tungsten(0) Complexes with P,S and P,Se Monooxidized Bis(phosphanyl)amine Ligands

Reactions of monooxidized thioyl and selenoyl bis(phosphanyl)amine ligands C₁₀H₇‐1‐N(P(E)Ph₂)(PPh₂) [E = S ( 1 ), Se ( 2 )] with Mo(CO)₄(pip)₂ and W(CO)₄(cod) afforded the complexes [M(CO)₄{ 1 ‐κ²P,S}] [M = Mo ( 3 ), W ( 4 )] and [M(CO)₄{ 2 ‐κ²P,Se}] [M = Mo ( 5 ), W ( 6 )]. Complexes 3 – 6 were characterized by multinuclear NMR (¹H, ¹³C, ³¹P, and ⁷⁷Se NMR) and IR spectroscopy. Crystal‐structure determinations were carried out on 3 , 5 , and 6 , which represent the first examples of structurally characterized complexes of such ligands with group‐6 metal carbonyls.     

Synthetic studies for the preparation of phosphorus carbonyl rhenacycles with the selenoimidodiphosphinate ligand [N(SePPh2)2]

The synthesis of the rhenacycles [Re(CO)₃(PR₃){Ph₂P(Se)NP(Se)Ph₂-κ²Se}], PR₃ = PPh₃ (1), PMePh₂ (2), and PMe₂Ph (3) by a straightforward high yield procedure is described. Attempts at the preparation of the spiro [Re(CO)₂(Ph₂PCH₂CH₂PPh₂-κ²P){Ph₂P(Se)NP(Se)Ph₂-κ²Se}] resulted in the formation of complexes [Re₂(CO)₆{Ph₂P(Se)NP(Se)Ph₂-κ²Se}₂(μ-Ph₂PCH₂CH₂PPh₂)] (4) and [Re(CO)₃(Ph₂PCH₂CH₂PPh₂-κ²P){Ph₂P(Se)NP(Se)Ph₂-κSe}] (5). All new inorganic rhenacycles 1-5 were characterized in solution and in solid state. The X-ray diffraction analysis of [Re(CO)₃PPh₃{Ph₂P(Se)NP(Se)Ph₂-κ²Se}] showed that its MnSePNPSe ring conformation is sensitive to temperature.     

Synthesis and Spectra of Cationic Bis(tertiary phosphine) derivatives of cycloheptatrienyliummolybdenum and cyclopentadienyliron complexes

Reaction of [(η-C₇H₇)Mo(CO)₃][PF₆] and [(η-C₅H₅)Fe(CO)₂CH₃CN][PF₆] with ditertiary phosphine ligands afforded products of three types; the monosubstituted complexes [(Ring)M(CO)₂Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1; Ring = η-C₅H₅, M = Fe, N = 1 and 2), the chelated complexes [(Ring)M(CO)Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1 and 2; Ring = η-C₅H₅, M = Fe, N = 1 and 2), and the dinuclear complex [{(η-C₇H₇)Mo(CO)₂}₂ -μ- Ph₂PCH₂CH₂PPh₂][(PF₆)₂]. Spectroscopic properties, including ³¹P NMR, are reported.     

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

Preparation and Crystal Structures of Dicyanamido(triphenylphosphane)gold(I) and Nitrosodicyanomethanido(triphenylphosphane)gold(I) The coordination compounds [(Ph₃P)Au{N(CN)₂}] ( 1 ) and [(Ph₃P)Au{ONC(CN)₂}] ( 2 ) are obtained by the reaction of [Au(PPh₃)]NO₃ with Na[N(CN)₂] or K[ONC(CN)₂] in CH₂Cl₂. 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, α = 115.327(10), β = 90.899(8), γ = 103.394(8)°, Z = 2. 2 crystallizes monoclinic in the space group P2₁/n with a = 832.59(10), b = 1139.30(16), c = 2078.9(4) pm, β = 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.