A new tridentate pincer phosphine/n-heterocyclic carbene ligand: palladium complexes, their structures, and catalytic activities

A new imidazolium salt, 1,3-bis(2-diphenylphosphanylethyl)-3H-imidazol-1-ium chloride (2), for the phosphine/N-heterocyclic carbene-based pincer ligand, PC(NHC)P, and its palladium complexes were reported. The complex, [Pd(PC(NHC)P)Cl]Cl (4), was prepared by the common route of silver carbene transfer reaction and a novel direct reaction between the ligand precursor, PC(NHC)P.HCl and PdCl(2) without the need of a base. Metathesis reactions of 4 with AgBF(4) in acetonitrile produced [Pd(PC(NHC)P)(CH(3)CN)](BF(4))(2) (5). The same reaction in the presence of excess pyridine gave [Pd(PC(NHC)P)(py)](BF(4))(2) (6). The X-ray structure determination on 4-6 revealed the chiral twisting of the central imidazole rings from the metal coordination plane. In solution, fast interconversion between left- and right-twisted forms occurs. The twisting reflects the weak pi-accepting property of the central NHC in PC(NHC)P. The uneven extent of twisting among the three complexes further implies the low rotational barrier about the Pd-NHC bond. Related theoretical computations confirm the small rotational energy barrier about the Pd-NHC bond (ca. 4 kcal/mol). Catalytic applications of 4 and 5 have shown that the complexes are modest catalysts in Suzuki coupling. The complexes were active catalysts in Heck coupling reactions with the dicationic complex 5 being more effective than the monocationic complex 4.     

Synthesis and structural characterisation of linear Au(I) N-heterocyclic carbene complexes: New analogues of the Au(I) phosphine drug Auranofin

The synthesis and characterisation of a series of neutral Au(I) N-heterocyclic carbene complexes [(NHC)AuX] (X = Cl and 2′,3′,4′,6′-tetra-O-acetyl-β-d-glucopyranosyl-1-thiolato) are reported. The chloro complexes were synthesised either by reaction of the appropriate 1,3-dialkylimidazol-2-ylidene with [(Me₂S)AuCl] or by transmetallation between the appropriate Ag(I)–NHC complex and [(Me₂S)AuCl]. The 2′,3′,4′,6′-tetra-O-acetyl-β-d-glucopyranosyl-1-thiolato complexes were prepared from the appropriate [(NHC)Au(I)Cl] complex and 2′,3′,4′,6′-tetra-O-acetyl-1-thio-β-d-glucopyranose under basic conditions. A cationic Au(I)–NHC triphenylphosphine adduct was also prepared. Structural studies (X-ray diffraction) of a number of the complexes show that in each case the gold atom is (quasi-) linearly two-coordinate, having C–Au–Cl, C–Au–S or C–Au–P coordination. In one case, a new phase of [(Cy₂Im)AuCl], the molecules pack pair-wise with a close Au⋯Au interaction (3.1566(6) Å). Preliminary studies show this complex is luminescent in the solid state.     

Preparation of Au(I), Ag(I), and Pd(II) N-heterocyclic carbene complexes utilizing a methylpyridyl-substituted NHC ligand. formation of a luminescent coordination polymer

Reaction of the imidazolium N-heterocyclic carbene precursor containing a methyl-substituted pyridyl functionality [HCH3im(CH3py)]PF6, 1, with Ag2O produces the homoleptic Ag(I) complex, [Ag(CH3im(CH3py))2]PF6, 2. In a simple carbene transfer reaction the analogous Au(I) species, [Au(CH3im(CH3py))2]PF6, 3, is formed by treatment of 2 with Au(tht)Cl in dichloromethane. Both 2 and 3 are structurally similar with nearly linearly coordinated NHC ligands. The methyl group appended to the pyridyl ring inhibits rotation of the pyridyl group at room temperature. Addition of AgBF4 to a hot propionitrile solution of 3 followed by crystallization with diethyl ether yields the one-dimensional coordination polymer, {[AuAg(CH3im(CH3py))2(NCCH2CH3)](BF4)2}n, 4, which contains Au-Ag separations of 2.9845(5) and 2.9641(5) A with intermetallic angles of 167.642(14) degrees and 162.081(9) degrees. This material is intensely luminescent in the solid state and exhibits an emission band at 453 nm (lambdaex=350 nm). Nearly colorless [Pd(CH3im(CH3py))2Cl]PF6, 5, is produced upon treatment of 2 with PdCl2(NCC6H5)2. The Pd(II) center in 5 is coordinated to one NHC ligand in a chelate fashion, while the second NHC is bound solely through the carbon center. The X-ray crystal structures of 1-5 are reported.     

Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(I)···Au(I) interactions: structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au2(NH2(CH2)2imMe)2][NO3]2

The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3-methylimidazolium nitrate, [NH(2)(CH(2))(2)imMe)]NO(3) ([3][NO(3)]) reacted with Ag(2)CO(3) in dimethyl sulfoxide readily yielding a Ag(I)-(NHC-NH(2)) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(I) complex [Au(2)(NH(2)(CH(2))(2)imMe)(2)][NO(3)](2) ([5][NO(3)](2)) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO(3)](2) have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations. Single-crystal structural studies showed that the Au(I)-carbene compound contains dinuclear (AuL)(2) cations in which pairs of gold(I) centres are linked by a pair of bridging ligands, with a Au···Au aurophilic contact of 3.2332(17) ? that is maintained in solution as documented by the DFT calculations. Complex [5][NO(3)](2) is photoluminescent in solution at room temperature and the high energy emission peak at 410 nm is remarkably shifted with respect to the absorption band centered at 260 nm.     

Solution and solid-state structure of the anion [Ag(2)[closo-CB(11)H(12)](4)](2-)

Addition of the carbene 1,3-dimesitylimidazol-2-ylidene (IMes) to a toluene solution of Ag[closo-CB(11)H(12)] results in the formation of the complex [(IMes)(2)Ag](2)[Ag(2)[closo-CB(11)H(12)](4)], the anionic component of which contains two silver(I) centers bridged by two carboranes in addition to one terminally bound carborane on each metal, in the solid-state. Comparison of the observed (11)B[(1)H] NMR chemical shifts of [(IMes)(2)Ag](2)[Ag(2)[closo-CB(11)H(12)](4)] or Ag[closo-CB(11)H(12)] with [NBu(4)][closo-CB(11)H(12)] in CD(2)Cl(2) demonstrates that the silver ion interacts significantly with the cage in solution. Theoretical investigations using the ab initio/GIAO/NMR method of [closo-CB(11)H(12)](-) and Na[closo-CB(11)H(12)] as model geometries for the silver salts support experimental evidence for these Ag...[BH] interactions in solution.     

Shorter argentophilic interaction than aurophilic interaction in a pair of dimeric {(NHC)MCl}(2) (M = Ag, Au) complexes supported over a N/O-functionalized N-heterocyclic carbene (NHC) ligand

Synthesis, structure, bonding, and photoluminescence studies of a pair of neutral dimeric silver and gold complexes of a N/O-functionalized N-heterocyclic carbene ligand exhibiting closed-shell d10...d10 argentophilic and aurophilic interactions, are reported. In particular, dimeric complexes of the type {[1-(benzyl)-3-(N-tert-butylacetamido)imidazol-2-ylidene]MCl}2 [M = Ag (2); Au (3)] displayed attractive metallophilic interaction in the form of a close ligand-unsupported metal...metal contact [3.1970(12) A in 2; 3.2042(2) A in 3] as observed from X-ray diffraction study and also was further verified by low temperature photoluminescence study at 77 K that showed the characteristic emission [527 nm for 2; 529 nm for 3] owing to the metal...metal interaction. The nature of the metallophilic interaction in these complexes was further probed using computational studies that estimated the metal...metal interaction energy to be 12.8 (2) and 8.6 kcal/mol (3). Notably, the argentophilic interaction was found to be stronger than the aurophilic interaction in this series of neutral dimeric complexes. The complexes 2 and 3 were synthesized sequentially, with the silver 2 complex prepared by the reaction of the 1-(benzyl)-3-(N-tert-butylacetamido)imidazolium chloride with Ag2O in 66% yield, while the gold 3 complex was obtained by the transmetallation reaction of the silver 2 complex with (SMe2)AuCl in 86% yield.     

Aurophilicity in gold(I) thiosemicarbazone clusters

The reaction of the phosphine thiosemicarbazone ligands HLPH and HLPMe with Au(I) ions yields the gold complexes [Au(3)(HLPH)(2)Cl(2)]Cl·2MeOH (1·2MeOH) and [Au(2)(HLPMe)Cl(2)] (2). The structures determined by X Ray diffraction, [Au(3)(HLPH)(2)Cl(2)]Cl·4MeOH (1·4MeOH) and [Au(2)(HLPMe)Cl(2)](2) (2), are the first examples of gold(I) thiosemicarbazone clusters showing aurophilicity. The structure of the trinuclear cation 1 contains the Au(1) atom located in an inversion centre, being connected to another gold(I) atom, Au(2), through a phosphino thiosemicarbazone molecule which acts as a S,P-bridging ligand. Additionally, every gold(I) atom in the trinuclear cation 1 assembles into trinuclear linear cluster units by means of close gold-gold interactions, being connected through the crystal cell in a 2D zigzag mode. The crystal structure of [Au(2)(HLPMe)Cl(2)](2) (2) contains one discrete molecule [(AuCl)(2)(HLPMe)] in the asymmetric unit, which is further assembled into tetranuclear [(AuCl)(2)(HLPMe)](2) units by means of close gold-gold interactions. Both clusters are highly luminescent in solution.     

Auration, argentation, and mercuration reactions of an iridaphosphirene

The reactions of the iridaphosphirene complex [Ir{=C(tBu)P(Cy)}(CO)(PPh3)2] (Cy = cyclohexyl) with either [AuCl(tht)] (tht = tetrahydrothiophene) or AgCl result in the products [Ir{=C(tBu)P[M(Cl)](Cy)}(CO)(PPh3)2], M = Au or Ag. The aurated product can additionally be obtained on reaction of the iridaphosphirene with [AuCl(CNtBu)], via loss of the isocyanide ligand. Treatment of [Ir{=C(tBu)P(Cy)}(CO)(PPh3)2] with [AuCl(PPh3)] in the presence of silver triflate leads to the isolation of the salt, [Ir{=C(tBu)P[Au(PPh3)](Cy)}(CO)(PPh3)2][SO3CF3]. Reaction of the iridaphosphirene with PhHgCl in the absence or presence of silver triflate affords the mercurated species [Ir{=C(tBu)P[Hg(Ph)](Cy)}(CO)(PPh3)2]X, X = Cl or CF3SO3, respectively. The former exhibits a weakly mercury-coordinated chloride ion. The X-ray crystal structures of all of the complexes are described.     

Gold and silver complexes with the ferrocenyl phosphine FcCH2PPh2

Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH2PPh2 [Fc = (eta5-C5H5)Fe(eta5-C5H4)] of the types [AuR(PPh2CH2Fc)], [M(PPh3)(PPh2CH2Fc)]OTf, and [M(PPh2CH2Fc)2]OTf (M = Au, Ag) have been obtained. Three-coordinate gold(I) and silver(I) derivatives of the types [AuCl(PPh2CH2Fc)2] and [M(PPh2CH2Fc)3]X (M = Au, X = ClO4; M = Ag, X = OTf) have been obtained from the corresponding gold and silver precursors in the appropriate molar ratio, although some of them are involved in equilibria in solution. The crystal structures of [AuR(PPh2CH2Fc)] (R = Cl, C6F5), [AuL(PPh2CH2Fc)]OTf (L = PPh3, FcCH2PPh2), [Au(C6F5)3(PPh2CH2Fc)], and [Ag(PPh2CH2Fc)3]OTf have been determined by X-ray diffraction studies.     

From large 12-membered macrometallacycles to ionic (NHC)2M+Cl- type complexes of gold and silver by modulation of the N-substituent of amido-functionalized N-heterocyclic carbene (NHC) ligands

A series of structurally diverse gold and silver complexes extending from ionic (NHC) 2M(+)Cl(-) (M=Au, Ag) type complexes to large 12-membered macrometallacycles have been prepared by the appropriate modification of the N-substituent of amido-functionalized N-heterocyclic carbenes. Specifically, the ionic, [1-(R)-3-{ N-(t-butylacetamido)imidazol-2-ylidene}]2M(+)Cl(-), (R=t-Bu, i-Pr; M=Au, Ag; 1b, 1c, 2b, 2c) complexes, were obtained in case of the N- t-butyl substituent of the amido-functionalized sidearm while 12-membered macrometallacycles, [1-(R)-3-{N-(2,6-di i-propylphenylacetamido)imidazol-2-ylidene}]2M2, (R=t-Bu, i-Pr; M=Au, Ag; 3b, 3c, 4b, 4c) were obtained in case of the 2,6-di i-propylphenyl N-substituent. These structurally diverse complexes of gold and silver were, however, prepared employing a common synthetic pathway involving the reactions of the imidazolium chloride salts (1a, 2a, 3a, 4a) with Ag2O to give the silver complexes (1b, 2b, 3b, 4b) and which, when treated with (SMe2)AuCl, gave the gold complexes (1c, 2c, 3c, 4c). Detailed density functional theory studies of 1b, 1c, 2b, 2c, 3b, 3c, 4b, and 4c were carried out to gain insight about the structure, bonding, and the electronic properties of these complexes. The NHC-metal interaction in the ionic 1b, 1c, 2b, and 2c complexes is primarily composed of the interaction of the carbene lone pair with the empty p orbital of the metal (5p for Ag and 6p for Au) while the same in the macrometallacyclic 3b, 3c, 4b, and 4c complexes consisted of the interaction of the carbene lone pair with the empty s orbital of the metal (5s for Ag and 6s for Au). The observation of a low energy emission in about the 580-650 nm region has been tentatively assigned to originate from the presence of weak metallophilic interaction in these macrometallacyclic 3b, 3c, 4b, and 4c complexes.     

(NHC)AuI]-catalyzed rearrangement of allylic acetates

[(NHC)AuCl] complexes (NHC = N-heterocyclic carbene), in conjunction with a silver salt, were found to efficiently catalyze the rearrangement of allylic acetates under both conventional and microwave-assisted heating. The optimization of several reaction parameters (solvent, silver salt, and ligand) as well as a study of the reaction scope are reported. The steric hindrance of the ligand bound to gold was found crucial for the outcome of the reaction as only extremely bulky ligands permitted the isomerization.     

Observing Initial Steps in Gold‐Catalyzed Alkyne Transformations by Utilizing Bodipy‐Tagged Phosphine–Gold Complexes

The Pd‐catalyzed reactions of 3‐chloro‐bodipy with R₂PH (R=Ph, Cy) provide nonfluorescent bodipy–phosphines 3‐PR₂–bodipy 3 a (R=Ph) and 3 b (R=Cy; quantum yield Φ<0.001). Metal complexes such as [AgCl( 3 b )] and [AuCl( 3 b )] were prepared and shown to display much higher fluorescence (Φ=0.073 and 0.096). In the gold complexes, the level of fluorescence was found to be qualitatively correlated with the electron density at gold. Consequently, the fluorescence brightness of [AuCl( 3 b )] increases when the chloro ligand is replaced by a weakly coordinating anion, whereas upon formation of the electron‐rich complex [Au(SR)( 3 b )] the fluorescence is almost quenched. Related reactions of [AuCl( 3 b )] with [Ag]ONf)] (Nf= nonaflate) and phenyl acetylenes enable the tracking of initial steps in gold‐catalyzed reactions by using fluorescence spectroscopy. Treatment of [AuCl( 3 b )] with [Ag(ONf)] gave the respective [Au(ONf)( 3 b )] only when employing more than 2.5 equivalents of silver salt. The reaction of the “cationic” gold complex with phenyl acetylenes leads to the formation of the respective dinuclear cationic [{( 3 b )Au}₂(CCPh)]⁺ and an increase in the level of fluorescence. The rate of the reaction of [Au(ONf)( 3 b )] with PhCCH depends on the amount of silver salt in the reaction mixture; a large excess of silver salt accelerates this transformation. In situ fluorescence spectroscopy thus provides valuable information on the association of gold complexes with acetylenes.     

新型氮杂环卡宾银(I)配合物的合成及其晶体结构

以取代苄氯(1a~1c)为起始原料,与咪唑经氮烷基化反应制得苄基咪唑氯盐(2a~2c); 2a~2c与氧化银经原位去质子化反应合成了3种新型的氮杂环卡宾银配合物--(NHC)AgCl［NHC: 1,3-二(4-甲氧基苄基)咪唑-2-亚基(3a), 1,3-二(3-甲氧基苄基)咪唑-2-亚基(3b)］和［(NHC)AgCl]₂［NHC=1,3-二(4-氯苄基)咪唑-2-亚基(3c)］,其结构经¹H NMR, ¹³C NMR, IR,元素分析和X-射线单晶衍射表征。3a~3c单晶结构均属单斜晶系,3a为P2₁/n空间群,3b和3c为P2₁/c空间群,3a和3b为单核银配合物,3c为双核银配合物。     

“Hummingbird” Behaviour of N‐Heterocyclic Carbenes Stabilises Out‐of‐Plane Bonding of AuCl and CuCl Units

An N‐heterocyclic carbene substituted by two expanded 9‐ethyl‐9‐fluorenyl groups was shown to bind an AuCl unit in an unusual manner, namely with the Au?X rod sitting out of the plane defined by the heterocyclic carbene unit. As shown by X‐ray studies and DFT calculations, the observed large pitch angle (21°) arises from an easy displacement of the gold(I) atom away from the carbene lone‐pair axis, combined with the stabilisation provided by weak CH???Au interactions involving aliphatic and aromatic H atoms of the NHC wingtips. Weak, intermolecular Cl???H bonds are likely to cooperate with the H???Au interactions to stabilise the out‐of‐plane conformation. A general belief until now was that tilt angles in NHC complexes arise mainly from steric effects within the first coordination sphere.     

Synthesis, structure and reactivity of palladium(II) complexes of chiral N-heterocyclic carbene-imine and -amine hybrid ligands

The synthesis and structures of chiral N-heterocyclic carbene (NHC)-N-donor complexes of silver(I) and palladium(II) are reported. The X-ray structure of an NHC-imine silver(I) complex [((nPr)CN(CHPh))AgBr](2) exhibits an Ag(2)Br(2) dimer motif where the imine group is not coordinated to the silver atom. Reaction between 2 and [PdCl(2)(MeCN)(2)] gives the palladium(II) complex [(kappa(2)-(nPr)CN(CHPh))PdCl(2)](3) that contains a chelating NHC-imine ligand as shown by single-crystal X-ray diffraction. Slow hydrolysis of related complexes [(kappa(2)-(nPr)CN(CHPh))PdCl(2)](3) and [(kappa(2)-((Ph)(2)CH)CN(CHPh))PdCl(2)](4) using triethylammonium chloride and water lead to the precipitation of single crystals of insoluble NHC-amino palladium(II) complexes [(kappa(2)-(nPr)CN(H(2)))PdCl(2)](6) and [(kappa(2)-((Ph)(2)CH)CN(H(2)))PdCl(2)](7), respectively. In the solid state, complexes 6 and 7 both exhibit intermolecular hydrogen bonding between chlorine and an amino-hydrogen atom resulting in an infinite chain structure. Substitution of an amino hydrogen for an ethyl group gives the soluble complex [(kappa(2)-(iPr)CN((H)Et))PdCl(2)](12). Reaction between two equivalents of 2 and [PdCl(2)(MeCN)(2)] gives the di-NHC complex [(kappa(1)-(nPr)CN(CHPh))(2)PdCl(2)](5) that does not contain a coordinated imine as shown by single crystal X-ray diffraction. Conproportionation between 5 and an equivalent of [PdCl(2)(MeCN)(2)] to does not occur at temperatures up to 100 degrees C in CD(3)CN.     

Gold(I) catalysts with bifunctional P, N ligands

A series of phosphanes with imidazolyl substituents were prepared as hemilabile PN ligands. The corresponding gold(I) complexes were tested as bifunctional catalysts in the Markovnikov hydration of 1-octyne, as well as in the synthesis of propargylamines by the three component coupling reaction of piperidine, benzaldehyde, and phenylacetylene. While the activity in the hydration of 1-octyne was low, the complexes are potent catalysts for the three component coupling reaction. In homogeneous solution the conversions to the respective propargylamine were considerably higher than under aqueous biphasic conditions. The connectivity of the imidazolyl substituents to the phosphorus atom, their substitution pattern, as well as the number of heteroaromatic substituents have pronounced effects on the catalytic activity of the corresponding gold(I) complexes. Furthermore, formation of polymetallic species with Au(2), Au(3), and Au(4) units has been observed and the solid-state structures of the compounds [(5)(2)Au(3)Cl(2)]Cl and [(3c)(2)Au(4)Cl(2)]Cl(2) (3c = tris(2-isopropylimidazol-4(5)-yl phosphane, 5 = 2-tert-butylimidazol-4(5)-yldiphenyl phosphane) were determined. The gold(I) complexes of imidazol-2-yl phosphane ligands proved to be a novel source for bis(NHC)gold(I) complexes (NHC = N-heterocyclic carbene).     

Novel scorpionate-type triscarbene ligands and their silver and gold complexes

New silver(I) carbene complexes were obtained starting from the N-heterocyclic carbene ligand precursors {[HB(RImH)₃]Br₂} (R = Bn, Mes and t-Bu) and {[HC(MeBImH)₃](BF₄)₃}, by treatment of the imidazolium salt with Ag₂O. Use of the tris-imidazolylborate precursors resulted in stable, well-characterized trimetallic complexes of general formula {Ag₃[HB(RIm)₃]₂}Br, which were successfully employed as carbene transfer reagents in the synthesis of related gold(I) complexes by transmetallation. The silver complexes also proved to be active catalysts of the coupling of aryl iodides with terminal alkynes (the Sonogashira reaction), although related bimetallic silver complexes were found to exhibit enhanced reactivity.     

Synthesis of Gold(I)−Trifluoromethyl Complexes and their Role in Generating Spectroscopic Evidence for a Gold(I)−Difluorocarbene Species

Readily prepared and bench-stable [Au(CF₃)(NHC)] compounds were synthesized by using new methods, starting from [Au(OH)(NHC)], [Au(Cl)(NHC)] or [Au(L)(NHC)]HF₂ precursors (NHC=N-heterocyclic carbene). The mechanism of formation of these species was investigated. Consequently, a new and straightforward strategy for the mild and selective cleavage of a single carbon/fluorine bond from [Au(CF₃)(NHC)] complexes was attempted and found to be reversible in the presence of an additional nucleophilic fluoride source. This straightforward technique has led to the unprecedented spectroscopic observation of a gold(I)−NHC difluorocarbene species.     

Amine-amide equilibrium in gold(III) complexes and a gold(III)-gold(I) aurophilic bond

The ligands HN(CH2-2-C5H4N)2, BPMA, and PhCH2N(CH2-2-C5H4N)2, BBPMA, react with Na[AuCl4] to give the cationic complexes [AuCl(BPMA-H)]+ and [AuCl(BBPMA)]2+, respectively. The amido complex [AuCl(BPMA-H)]+ undergoes easy inversion at the amido nitrogen atom and can be reversibly protonated by triflic acid to give [AuCl(BPMA)]2+. The complex [AuCl(BBPMA)]2+ is easily decomposed in aqueous solution by cleavage of a carbon-nitrogen bond or, in dilute HCl solution, by protonation of the ligand to give [BBPMAH2]Cl[AuCl4] The complexes [BBPMAH2]Cl[AuCl4] and [BBPMAH2]Cl[AuCl2] can be formed by direct reaction of BBPMA with H[AuCl4]. Unusual forms of gold(III)...gold(III) and gold(III)...gold(I) aurophilic bonding are observed in the salts [AuCl(BPMA-H)][PF6] and [AuCl(BPMA-H)][AuCl2], respectively. The first comparison of the structures of gold(III) amine and amido complexes, in the cations [AuCl(BPMA-H)]+ and [AuCl(BPMA)]2+, indicates that there is little ppi-dpi bonding in the amido-gold bond and that the amide exerts a stronger trans influence than the amine group.     

新型含丙腈基和咪唑基三脚架配体-银(Ⅰ)配合物的合成与结构

设计合成了同时含有丙腈基和咪唑基的新型三脚架配体N,N-二(3-丙腈基)-[3-(1-咪唑基)]正丙胺(L),并与银盐按1:1和2:1的比例反应分别得到了配合物{[AgL]X}n (X = BF4-,1a;X = ClO4-,1b)和{[Ag(L)2]ClO4}n(2),并用X-射线单晶结构分析和电喷雾质谱等方法对其进行了表征。结构分析结果表明,配合物1a和1b为一维链状结构,而配合物2则为单核结构。表明金属盐和配体的比例对配合物结构有很大影响。