Methanide Complexes Research Articles

Correlating axial and equatorial ligand field effects to the single-molecule magnet performances of a family of dysprosium bis-methanediide complexes.

Treatment of the new methanediide–methanide complex [Dy(SCS)(SCSH)(THF)] (1Dy, SCS = {C(PPh2S)2}2−) with alkali metal alkyls and auxillary ethers produces the bis-methanediide complexes [Dy(SCS)2][Dy(SCS)2(K(DME)2)2] (2Dy), [Dy(SCS)2][Na(DME)3] (3Dy) and [Dy(SCS)2][K(2,2,2-cryptand)] (4Dy). For further comparisons, the bis-methanediide complex [Dy(NCN)2][K(DB18C6)(THF)(toluene)] (5Dy, NCN = {C(PPh2NSiMe3)2}2−, DB18C6 = dibenzo-18-crown-6 ether) was prepared. Magnetic susceptibility experiments reveal slow relaxation of the magnetisation for 2Dy–5Dy, with open magnetic hysteresis up to 14, 12, 15, and 12 K, respectively (∼14 Oe s−1). Fitting the alternating current magnetic susceptibility data for 2Dy–5Dy gives energy barriers to magnetic relaxation (Ueff) of 1069(129)/1160(21), 1015(32), 1109(70), and 757(39) K, respectively, thus 2Dy–4Dy join a privileged group of SMMs with Ueff values of ∼1000 K and greater with magnetic hysteresis at temperatures >10 K. These structurally similar Dy-components permit systematic correlation of the effects of axial and equatorial ligand fields on single-molecule magnet performance. For 2Dy–4Dy, the Dy-components can be grouped into 2Dy–cation/4Dy and 2Dy–anion/3Dy, where the former have almost linear C Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> DyC units with short average DyC distances, and the latter have more bent CDyC units with longer average DyC bonds. Both Ueff and hysteresis temperature are superior for the former pair compared to the latter pair as predicted, supporting the hypothesis that a more linear axial ligand field with shorter M–L distances produces enhanced SMM properties. Comparison with 5Dy demonstrates unusually clear-cut examples of: (i) weakening the equatorial ligand field results in enhancement of the SMM performance of a monometallic system; (ii) a positive correlation between Ueff barrier and axial linearity in structurally comparable systems.

Methanediide Formation via Hydrogen Elimination in Magnesium versus Aluminium Hydride Complexes of a Sterically Demanding Bis(iminophosphoranyl)methanediide

Substituted bis(iminophosphoranyl)methanes are CH acidic compounds that can form complexes with formally dianionic central carbon centres. The reaction of H2C(Ph2P=NDip)2 (≡ H2L), Dip = 2,6-diisopropylphenyl, with one equivalent of di-n-butylmagnesium afforded the methanide complex [HLMgnBu] 1. Treatment of Complex 1 with phenylsilane in aromatic solvents at elevated temperatures afforded the methanediide complex [(LMg)2] 2 presumably via the MgH intermediate [(HLMgH)n] (n = 1 or 2). The reaction of 1 with LiAlH4 in diethyl ether yielded the AlH complex [HLAlH2] 3. Alternatively, this complex was also obtained from the reaction of H2L with AlH3∙NMe3. The molecular structures of [HLMgnBu] 1, [(LMg)2] 2, and [HLAlH2] 3 are reported. Complex 3 shows no sign of H2 elimination to a methanediide species at elevated temperatures in contrast to the facile elimination of the putative reaction intermediate [(HLMgH)n] (n = 1 or 2) to form [(LMg)2] 2. The chemical properties of Complex 2 were investigated, and this complex appears to be stable against coordination with strong donor molecules.

A combined experimental and quantum chemical study on thallium(I) tris(pyrazolyl)methanide

Density functional theory methods have been applied to identify the favoured structural motif of thallium(I) tris(pyrazolyl)methanide complexes. The reaction of [TlN(SiMe3)2]2 with tris(pyrazolyl)methane HC(pz)3 (with pz=pyrazolyl) in toluene furnished the highly air-sensitive title compound [Tl(HTpmd)] (4) (with HTpmd=[C(pz)3]−). An X-ray diffraction study revealed that complex 4 consists of a single bond between the thallium(I) cation and the carbanion of HTpmd ligand entity. This Tl–C bond (254.1(8)pm) is supported by two additional Tl⋯N contacts (Tl⋯N: 273.6(7) and 293.1pm) provided by the N donor atoms of two pyrazolyl scaffolds of the tripodal ligand. Overall, a κ2N,κ1C coordination mode of the tris(pyrazolyl)methanide ligand is at hand in complex 4. Furthermore, the title compound forms a weak dimer in the solid-state by additional intermolecular Tl⋯N′ interactions (318.7pm).

Front Cover: Synthesis and Structural Characterization of Mono‐ and Bimetallic Rhodium(I), Iridium(I) and Gold(I) Methanide and Methandiide Complexes from 2‐Quinolyl‐Linked (Thiophosphoranyl)methane (Eur. J. Inorg. Chem. 24/2016)

Front Cover: Synthesis and Structural Characterization of Mono‐ and Bimetallic Rhodium(I), Iridium(I) and Gold(I) Methanide and Methandiide Complexes from 2‐Quinolyl‐Linked (Thiophosphoranyl)methane (Eur. J. Inorg. Chem. 24/2016)

An extremely bulky tris(pyrazolyl)methanide: a tridentate ligand for the synthesis of heteroleptic magnesium(II) and ytterbium(II) alkyl, hydride, and iodide complexes.

The tris(pyrazolyl)methane compound HC(3-Ad-5-Mepz)3 [1, 3-Ad-5-Mepz=3-(1-adamantyl)-5-methylpyrazolyl] and its regioisomer, HC(3-Ad-5-Mepz)2 (3-Me-5-Adpz), were synthesized and crystallographically characterized. Deprotonation of 1 with MeLi afforded the lithium complex [{κ(3) -N-C(3-Ad-5-Mepz)3 }Li(thf)], which incorporates a tris(pyrazolyl)methanide ligand of unprecedented bulk. Reaction of 1 with MeMgI gave the ionic coordination complex [{κ(3) -N-HC(3-Ad-5-Mepz)3 }MgMe]I, which was readily deprotonated to afford the neutral compound [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgMe]. The related magnesium butyl compound [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgBu] was prepared from the reaction of 1 and MgBu2 . Treating this with LiAlH4 or LiAlD4 led to rare examples of terminal magnesium hydride/deuteride complexes, [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgH/D]. All neutral magnesium alkyl and hydride compounds were crystallographically authenticated. Reaction of [{κ(3) κN-C(3-Ad-5-Mepz)3 }Li(thf)] with [YbI2 (thf)2 ] yielded the first structurally characterized f-block tris(pyrazolyl)methanide complex, [{κ(3) -N-C(3-Ad-5-Mepz)3 }YbI(thf)].

Synthesis and Structural Characterization of Base-Stabilized Oligomeric Heterovinylidenes

Metalation of the (iminophosphoranyl)phosphine PPh2CH2(PPh2═NSiMe3) (1) with an equimolar amount of n-BuLi afforded the monolithium salt [Li{CH(PPh2)(PPh2═NSiMe3)}(THF)2] (2). The reaction of 2 with GeCl2·1,4-dioxane has led to the formation of a germavinylene moiety, which trimerized to form a new heterocyclic cage compound, [{(PPh2═NSiMe3)(PPh2)C═Ge:}{(PPh2═NSiMe3)(PPh2)C}2Ge→Ge:] (3). A similar reaction of the lithium methanide complex 2 with SnCl2 afforded the stannavinylidene moiety, which underwent a "head-to-tail" cycloaddition to form a stable 1,3-distannacyclobutane, 4. A trapping reaction of 4 with diiron nonacarbonyl gave the novel iron stannavinylidene complex 5. The solid-state structure analysis of 5 reveals that it contains two stannavinylidene moieties bonded in a Sn-P "head-to-tail" fashion, with one of the tin(II) centers coordinating to a Fe(CO)4 moiety. The X-ray structures of 2-5 have been determined by X-ray crystallography. In addition, the dynamic behavior of 5 has been studied by means of variable-temperature (31)P and (119)Sn NMR spectroscopy.

{CH2(PPh2=NSiMe3)(PPh2=S)} and {CH(PPh2=NSiMe3)(Ph2P=S)}– as Ligands in Zinc Chemistry: Synthesis and Structures

AbstractThe (iminophosphoranyl)(thiophosphoranyl)methane zinc complexes [{(PPh2=NSiMe3)(PPh2=S)CH2}ZnX2] (X = Cl, I) have been obtained by the reaction of {CH2(PPh2=NSiMe3)(PPh2=S)} with the corresponding zinc dihalides ZnCl2 and ZnI2. The (iminophosphoranyl)(thiophosphoranyl)methane ligand coordinates as a bidentate ligand through the nitrogen and sulfur atoms to the zinc atom to form a six‐membered metallacycle (N–P–C–P–S–Zn). The reaction of {CH2(PPh2=NSiMe3)(PPh2=S)} with [Zn{N(SiMe3)2}2] and ZnPh2 resulted in the (iminophosphoranyl)(thiophosphoranyl)methanide complexes [{(PPh2=NSiMe3)(PPh2=S)CH}Zn{N(SiMe3)2}] and [{(PPh2=NSiMe3)(PPh2=S)CH}ZnPh], respectively. In addition to the coordination of the phosphinimine nitrogen and sulfur atoms to the zinc atom, a long contact between the methine carbon atom of the P–C–P bridge and the zinc atom was observed in these complexes. The solid‐state structures of all the new compounds were established by single‐crystal X‐ray diffraction.

Reactivity Studies of a T-Shaped Yttrium Carbene: C–F and C–O Bond Activation and C═C Bond Formation Promoted by [Y(BIPM)(I)(THF)2] (BIPM = C(PPh2NSiMe3)2)

The yttrium carbene complex [Y(BIPM)(I)(THF)2] (1; BIPM = C(PPh2NSiMe3)2) was reacted with a range of unsaturated substrates. The reaction of 1 with the phosphaalkyne PCBut afforded the [2 + 2] cycloaddition product [Y{C(PPh2NSiMe3)2(PCBut)-κ4C,C′,N,N′}(I)] (2). Similarly, the reactions of 1 with the heteroallenes N,N′-dicyclohexylcarbodiimide and tert-butyl isocyanate gave the [2 + 2] cycloaddition products [Y{C(PPh2NSiMe3)2[C(NCy)2]-κ4C,N,N′,N″}(I)(THF)] (3) and [Y{C(PPh2NSiMe3)2[C(O)(NBut)]-κ4C,N,N′,O}(I)(THF)2] (4), respectively. In contrast, the reaction of 1 with tert-butyl isothiocyanate afforded the ketenimine ButN═C═C(PPh2NSiMe3)2 (5), with the concomitant formal elimination of “YSI(THF)n”. The sterically demanding arylamine 2,6-diisopropylphenylamine reacted with 1 via a 1,2-addition across the Y═C bond to yield the anilide–methanide complex [Y(BIPMH)(NHDipp)(I)(THF)] (6; Dipp = C6H3Pri2-2,6). The reaction of 1 with the benzopyrone coumarin affords the ring-opened dinuclear aryloxide–enolate complex [Y2{C(PPh2NSiMe3)2[C(O)(CHCHC6H4O-2)]-κ2-N,O:μ,κ-O′}2(I)(μ-I)(THF)] (7), which is postulated to form by sequential Y–O, C–C, and C═C bond formation and cleavage of the C–O ester linkage and the C═O and Y═C double bonds. Benzoyl fluoride reacts with 1 to afford 1/2 equiv of the bis-enolate complex [Y{C(PPh2NSiMe3)2[C(O)(Ph)]-κ2N,O}2(I)] (8) with formal elimination of “YF2I(THF)n” by ligand scrambling. Complexes 2–8 have been characterized by X-ray crystallography, multielement NMR spectroscopy, FTIR spectroscopy, and CHN microanalyses.

Aluminium Complexes of a Sterically Demanding Bis(iminophosphorane)methandiide

The reaction of the sterically demanding bis(iminophosphorane)methane, {DipN=P(Ph2)}2CH2, H2L 1 (where Dip = 2,6-iPr2C6H3), with one or two equivalents of AlMe3 in toluene under varying conditions led to the methanide complex [HLAlMe2] 4, and the methandiide complex [L(AlMe2)2] 5, respectively. Iterative iodination of complex 5 with I2 in toluene yielded the complexes [L(AlMeI)2] 6 and [L(AlI2)2] 7. The complexes 4–7 were structurally characterised. The methanide 4 forms a puckered six-membered ring without Al-C(methanide) contact and the complexes 5 and 6 show coordination of the methandiide ligand to two Al atoms forming two four-membered rings on the central spirocyclic carbon centre. Complex 7 shows an asymmetric coordination mode of the two Al centres to the methandiide ligand in the solid state with an almost planar, severely distorted three-coordinate methandiide carbon atom and only one short Al–C bond.

Investigations on the Steric Accessibility of the Carbanionic Moiety in Zwitterionic Magnesium Tris(pyrazolyl)methanide Complexes. Synthesis and Characterisation of Bi‐ and Tri­metallic Complexes

AbstractReactions of HC(pz)3 and HC(4‐Mepz)3 with MgBu2 and Mg{N(SiMe3)2}2 gave the zwitterionic complexes [Mg{C(pz)3}2] (2) and [Mg{C(4‐Mepz)3}2] (4), respectively, containing “free” pyramidal carbanions (pz = pyrazolyl). The solid‐state structure of 2 has been determined. Reactions of 2 and 4 as well as the recently reported homo‐ and heteroleptic complexes [Mg{C(3, 5‐Me2pz)3}2] (1) and [Mg{C(3, 5‐Me2pz)3}{C(pz)3}] (3) with the Lewis acid AlEt3 furnished the bi‐ and trimetallic complexes [Mg{C(pz)3}2(AlEt3)2] (5), [Mg{C(pz)3}(AlEt3){C(3, 5‐Me2pz)3}] (6), and [Mg{C(4‐Mepz)3}2(AlEt3)2] (7). Based on NMR spectroscopic investigations, including an X‐ray structural analysis on single crystals of 5, only the parent tris(pyrazolyl)methanide {C(pz)3}– and the 4‐methyl‐substituted ligand scaffolds form C‐bound adducts with the Lewis acid. By quantifying the steric bulk of κ3N‐coordinated {C(pz)3}– it could be shown that its steric features are similar to those of bulky phosphine ligands.

Synthesis of a Uranium(VI)-Carbene: Reductive Formation of Uranyl(V)-Methanides, Oxidative Preparation of a [R2C═U═O]2+Analogue of the [O═U═O]2+Uranyl Ion (R = Ph2PNSiMe3), and Comparison of the Nature of UIV═C, UV═C, and UVI═C Double Bonds

We report attempts to prepare uranyl(VI)- and uranium(VI) carbenes utilizing deprotonation and oxidation strategies. Treatment of the uranyl(VI)-methanide complex [(BIPMH)UO(2)Cl(THF)] [1, BIPMH = HC(PPh(2)NSiMe(3))(2)] with benzyl-sodium did not afford a uranyl(VI)-carbene via deprotonation. Instead, one-electron reduction and isolation of di- and trinuclear [UO(2)(BIPMH)(μ-Cl)UO(μ-O){BIPMH}] (2) and [UO(μ-O)(BIPMH)(μ(3)-Cl){UO(μ-O)(BIPMH)}(2)] (3), respectively, with concomitant elimination of dibenzyl, was observed. Complexes 2 and 3 represent the first examples of organometallic uranyl(V), and 3 is notable for exhibiting rare cation-cation interactions between uranyl(VI) and uranyl(V) groups. In contrast, two-electron oxidation of the uranium(IV)-carbene [(BIPM)UCl(3)Li(THF)(2)] (4) by 4-morpholine N-oxide afforded the first uranium(VI)-carbene [(BIPM)UOCl(2)] (6). Complex 6 exhibits a trans-CUO linkage that represents a [R(2)C═U═O](2+) analogue of the uranyl ion. Notably, treatment of 4 with other oxidants such as Me(3)NO, C(5)H(5)NO, and TEMPO afforded 1 as the only isolable product. Computational studies of 4, the uranium(V)-carbene [(BIPM)UCl(2)I] (5), and 6 reveal polarized covalent U═C double bonds in each case whose nature is significantly affected by the oxidation state of uranium. Natural Bond Order analyses indicate that upon oxidation from uranium(IV) to (V) to (VI) the uranium contribution to the U═C σ-bond can increase from ca. 18 to 32% and within this component the orbital composition is dominated by 5f character. For the corresponding U═C π-components, the uranium contribution increases from ca. 18 to 26% but then decreases to ca. 24% and is again dominated by 5f contributions. The calculations suggest that as a function of increasing oxidation state of uranium the radial contraction of the valence 5f and 6d orbitals of uranium may outweigh the increased polarizing power of uranium in 6 compared to 5.

A Well‐Defined Silica‐Supported Lanthanum Bis(phosphinimino)methanide

AbstractGrafting of the bis(phosphinimino)methanide complex [La{CH(PPh2NSiMe3)2}{N(SiHMe2)2}2] (1) onto dehydroxylated silica (SiO2‐700) affords material 2. Full characterization of this material by infrared spectroscopy, elemental analysis, and multinuclear, multidimensional solid‐state NMR spectroscopy showed formation of well‐defined bis(phosphinimino)methanide amido surface species, [(≡SiO)La{CH(PPh2NSiMe3)2}{N(SiHMe2)2}], along with [≡SiOSiHMe2] sites.

ChemInform Abstract: Ring Expansion of Spirocyclic Germanium(II) Di(phosphanyl)methanide Complexes by Insertion of Sulfur and Selenium into Germanium- Phosphorus Bonds.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Bis(phosphinimino)methanides as non-innocent ligand in zinc chemistry: synthesis and structures

Reactions of the bis(phosphinimino)methane {CH2(Ph2PNSiMe3)2} with the zinc dihalides ZnCl2 and ZnI2 afforded the corresponding bis(phosphinimino)methane complexes [{(Me3SiNPPh2)2CH2}ZnCl2] (1) and [{(Me3SiNPPh2)2CH2}ZnI2] (2). In contrast, treatment of {CH2(Ph2PNSiMe3)2} with ZnPh2 in toluene gave the bis(phosphinimino)methanide complex of [{(Me3SiNPPh2)2CH}ZnPh] (3). Further reaction of 3 with the heterocumulenes di(p-tolyl)carbodiimine and diphenyl ketene resulted via a nucleophilic addition of the methine carbon atom of the {CH(Ph2PNSiMe3)2}- ligand to the heterocumulenes in a C-C bond formation. New tripodal phenyl zinc complexes of composition [{(Me3SiNPPh2)2CH)(p-Tol)NC-N(p-Tol)}ZnPh] (4) and [{(Me3SiNPPh2)2CH)(Ph2CC-O)}ZnPh] (5) were obtained.

Bis(phosphinimino)methanides as Ligands in Divalent Ytterbium and Strontium Chemistry–Synthesis and Structure

AbstractTwo new bis(phosphinimino)methanide complexes of divalent ytterbium, [{(Me3SiNPPh2)2CH}2Yb], and strontium, [{(Me3SiNPPh2)2CH}2Sr], were synthesized from the corresponding metal diiodides and of K{CH(PPh2NSiMe3)2}. Alternatively, the ytterbium compound could also be obtained starting from [{(Me3SiNPPh2)2CH}YbI(THF)2]. A comparison of the properties with the analogues compounds [{(Me3SiNPPh2)2CH}2M] (M = Ca, Ba, Sm, Eu) is given.

Lithium, Magnesium, and Zinc Iminophosphorano(8-quinolyl)methanide Complexes: Syntheses, Characterization, and Activity in ε-Caprolactone Polymerization

Lithiation of R2P(CH2C9H6N-8)NBut (R = Ph, 3; R = Pri, 4) with an equivalent of BunLi afforded lithium iminophosphorano(8-quinolyl)methanide [Li{CH(8-C9H6N)P(Ph2)NBut}(THF)] (5) and [Li{CH(8-C9H6N)P(Pri2)NBut}]2 (6), respectively. Reaction of 4 with Et2Mg yielded magnesium iminophosphorano(8-quinolyl)methanide complex (7). Treatment of 6 with ZnCl2 gave [Zn(Cl){CH(8-C9H6N)P(Pri2)NBut}] (8), which was transformed into alkylated zinc complexes [Zn(R1){CH(8-C9H6N)P(Pri2)NBut}] (R1 = Ph, 9; R1 = Me, 10) by treating with R1Li or R1MgX. Ethylzinc complexes [Zn(Et){CH(8-C9H6N)P(R2)NBut}] (R = Ph, 11; R = Pri, 12) were obtained by reaction of 3 or 4 with an equivalent of Et2Zn. Compounds 2 and 4−12 were characterized by 1H, 13C{1H}, and 31P{1H} NMR spectroscopy and elemental analyses. Structures of complexes 6−8 and 10 were further characterized by single-crystal X-ray diffraction techniques. The catalytic behaviors of complexes 7 and 9−12 in the ring-opening polymerization of ε-caprolactone was studied. Complex 7 exhibited high catalytic activity in the presence or absence of benzyl alcohol. Complexes 9−12 catalyzed the ring-opening polymerization of ε-CL in the presence of benzyl alcohol and exhibited first-order dependence on monomer concentration.

Group 11 Complexes with the Bidentate (SePPh2)2CH2 and Tridentate [(SePPh2)2CH]– Ligands

The reaction of (SePPh2)2CH2 with group 11 metal complexes such as [Au(C6F5)3(tht)] (tht = tetrahydrothiophene) affords the complex [Au(C6F5)3(SePPh2CH2PPh2Se)] in which the ligand coordinates to the gold(III) center only through one selenium atom. The treatment of the ligand with Ag(OTf) or [Cu(NCMe)4]PF6 leads, depending on the molar ratio, to the complexes [Ag2{(SePPh2)2CH2}2](OTf)2 or [M{(SePPh2)2CH2}2]X (M = Ag, X = OTf; M = Cu, X = PF6; OTf = CF3SO3) in which the phosphine selenide ligand coordinates as a bidentate bridging or chelating ligand through the Se,Se atoms. The reaction of (SePPh2)2CH2 with [Au(C6F5)2(acac)] (acac = acetylacetonate) occurs with deprotonation of the methylene group, and the methanide complex, [Au(C6F5)2(SePPh2CHPPh2Se)], is obtained, with a bidentate chelate Se,C coordination to the gold(III) center. The selenium atom can react further with other metal complexes such as [Au(C6F5)3(tht)] to give the dinuclear species [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}], in which the ligand coordinates in a tridentate Se,C,Se form. The crystal structure of [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}] has been established by X-ray diffraction.

In Situ Formation of Bis(phosphinimino)methanide Rare Earth Alkoxide Initiators for the Ring-Opening Polymerization of ε-Caprolactone

A series of pentamethylcyclopentadienyl bis(phosphinimino)methanide complexes of yttrium and the lanthanides, [{CH(PPh2NSiMe3)2}Ln(η5-C5Me5)Cl] (Ln = Y (1a), Sm (1b), Yb (1c)), were prepared by two...

Reactivity of an N-mesityl bis(phosphinimino)methane with group 10 metals

In an attempt to form a group 10 ‘carbenoid’ derivative by double deprotonation of the N-mesityl substituted bis(phosphinimino)methane [CH 2(Ph 2P N-2,4,6-Me 3C 6H 2) 2], reaction with [PdCl 2(MeCN) 2] yielded a singly metallated dichloropalladate(II) complex as the only product. This was completely characterised specroscopically and by single crystal crystal X-ray diffraction. In contrast, reaction of [CH 2(Ph 2P N-2,4,6-Me 3C 6H 2) 2] with [PtMe 2(COD)] produced a bis(phosphinimino)methanide complex, which had also undergone ortho-metallation of two P-phenyl groups to effect a triple C–H activation reaction.

Reactions of Potassium Bis(phosphinimino)methanide with Group 11 Compounds

Transmetalation of the potassium methanide complex, K{CH(PPh2NSiMe3)2}, with [(Ph3P)2CuI] afforded the corresponding copper complex [{CH(PPh2NSiMe3)2}CuPPh3] (1), whereas the reaction of K{CH(PPh2NSiMe3)2} with [Ph3PAuCl] resulted in the dinuclear gold complex [(Ph3PAu)2{C(PPh2NSiMe3)2}] (2). The solid-state structure of 1 shows the formation of a six-membered metallacycle (N1-P1-C1-P2-N2-Cu) that has a twist boat conformation. In contrast, compound 2 is an alpha,alpha-diaurated species, in which the two gold atoms are coordinated in a linear fashion onto the ligand backbone. Photoluminescence measurements show that the latter compound has a strong violet emission.