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C6Me3(C&tbd1;CH)3-1,3,5 (Ar(C&tbd1;CH)3) reacts with [AuCl(SMe2)] and NEt3 (1:3:3) to give [Au3{μ-(C&tbd1;C)3Ar}]n (1). Complexes of the general formula [{AuL}3{μ-(C&tbd1;C)3Ar}] can be obtained from 1 and excess isocyanide (L = ^tBuNC (2), XyNC (3)), by treating 2 with an excess of NHEt2 (L = C(NH^tBu)NEt2 (4)), or by reacting [Ar(C&tbd1;CH)3] with [Au(acac)PPh3] (1:3, L = PPh3 (5)) or with PPN[AuCl2] (1:3, PPN = Ph3P&dbd;N&dbd;PPh3) and an excess of NHEt2 (L = NHEt2 (6)). The reaction of C6Me4(C&tbd1;CH)2-1,4 (Ar‘(C&tbd1;CH)2) with PPN[AuCl2] (1:2) and an excess of NHEt2 gives [{AuNHEt2}2{μ-(C&tbd1;C)2Ar‘}] (7), which reacts with 1,6-bis(diphenylphosphino)hexane (dpph) to give [Au2{μ-(C&tbd1;C)2Ar‘}(μ-dpph)]n (8). The reactions of the alkynes [Ar(C&tbd1;CH)3], [Ar‘(C&tbd1;CH)2], and ToC&tbd1;CH (To = 4-MeC6H4) with the appropriate amounts of PPN[Au(acac)2] (acac = acetylacetonato) allow the syntheses of the anionic complexes PPN[Au{C&tbd1;CAr(C&tbd1;CH)2}2] (9), PPN[Au{C&tbd1;CAr‘C&tbd1;CH}2] (10), PPN[Au{C&tbd1;CTo}2] (11), (PPN)3n[Au{C&tbd1;CAr(C&tbd1;C)2}2Au2]n (12), and (PPN)n[Au{μ-(C&tbd1;C)2Ar‘}]n (13). The X-ray crystal structures of 5, 9, and 11 have been determined.

C6Me4(C&tbd1;CH)2-1,2 [Ar(C&tbd1;CH)2] reacts with PPN[Au(acac)2] (acac = acetylacetonato, PPN = (Ph3P)2N) (2:1) or with [AuCl(SMe2)] and NEt3 (1:2:2) to give PPN[Au{C&tbd1;CArC&tbd1;CH}2] (1) or [Au2{μ-Ar(C&tbd1;C)2})]n (2), respectively. Dinuclear complexes of general formula [Au2L2{μ-Ar(C&tbd1;C)2}] can be obtained by reacting 2 with the appropriate ligand L (1:2) [L = ^tBuNC (3), PMe3 (4), PTo3 (5, To = C6H4Me-4)] or L2 (1:1) (L2 = Ph2P(CH2)nPPh2, n = 4 (6), 6 (7)]. The analogous complexes [(AuNHEt2)2{μ-Ar(C&tbd1;C)2}] (8) and [{AuC(NH^tBu)(NEt2)}2{μ-Ar(C&tbd1;C)2}] (9) result from the reactions of Ar(C&tbd1;CH)2 with PPN[AuCl2] and NHEt2 (1:2:4) or 3 with an excess of NHEt2, respectively. The reaction of 5 with AgClO4 (2:1) gives the heteropentanuclear “AgAu4” complex [Ag{(AuPTo3)2{μ-Ar(C&tbd1;C)2}}2]ClO4 (10). The X-ray crystal structures of 3, 7, 9·1/3CHCl3, and 10·2CHCl3 have been determined.

The alkynes C6Me4(C&tbd1;CH)2-1,4, C6Me4(C&tbd1;CH)2-1,2, and C6Me3(C&tbd1;CH)3-1,3,5 react with cis-[PtCl2(PAr3)2] and NHEt2 and a catalytic amount of CuI to give complexes trans-[Pt(C&tbd1;CC6Me4C&tbd1;CH-4)2(PAr3)2] [Ar = Ph (1a), C6H4Me-4 (To) (1b)], trans-[Pt(C&tbd1;CC6Me4C&tbd1;CH-2)2(PAr3)2] [Ar = Ph (2a), To (2b)], and trans-[Pt{C&tbd1;CC6Me3(C&tbd1;CH)2-3,5}2(PAr3)2] [Ar = Ph (3a), To (3b)], respectively. The reactions of [Au(acac)PAr3] (acac = acetylacetonato) with complex 1a or 1b (2:1) or with 3b (4:1) give the neutral mixed Pt^IIAu^I2 or Pt^IIAu^I4 σ-alkynyl complexes trans-[Pt(C&tbd1;CC6Me4C&tbd1;CAuPAr3-4)2(PAr3)2] [Ar = Ph (4a), To (4b)] or trans-[Pt{C&tbd1;CC6Me3(C&tbd1;CAuPTo3)2-3,5}2(PTo3)2] (5b), respectively. Additionally, the replacement of the triarylphosphine ligands present in 1a, 2a, 4b, or 5b with various trialkylphosphines produces the homologous derivatives with PMe3 (1c, 2c, 4c, 5c), PEt3 (1d), or P(ⁿBu)3 (1e), respectively. PPN[Au(acac)2] reacts with complex 1a, 1c, or 1e (1:1) to give (PPN)n[trans-Pt{(C&tbd1;CC6Me4C&tbd1;C-4)2Au}(PR3)2]n [R = Ph (6a), Me (6c), ⁿBu (6e)], while its reaction with 3b (2:1) produces (PPN)2n[trans-Pt{C&tbd1;CC6Me3(C&tbd1;C)2-3,5Au2(PTo3)2]n (7). Complexes 6a, 6c, 6e, and 7 are the first anionic σ-alkynyl metal polymers described so far. The crystal structures of 1a·CHCl3, 2b·2CHCl3, and 4b·5CH2Cl2 have been determined. Each complex displays crystallographic inversion symmetry.

The reactions of 3,5-diethynylpyridine (Py(C&tbd1;CH)2) with PPN[Au(acac)2] (2.5:1; PPN = Ph3P&dbd;N&dbd;PPh3) or with [AuCl(SMe2)] and NEt3 (1:2:2) give respectively PPN[Au{C&tbd1;C(Py)C&tbd1;CH}2] (1) and [Au2{μ-(C&tbd1;C)2Py}]n (2). Complex 2 reacts with monodentate ligands (1:2) or with 1,6-bis(diphenylphosphino)hexane (dpph, 1:1) to give neutral dinuclear complexes of the general formula [(AuL)2{μ-(C&tbd1;C)2Py}] (L = CN^tBu (3), PMe3 (4), PPh3 (5), PTo3 (To = C6H4Me-4) (6); Au2L2 = Au2(μ-dpph) (7)). The reactions of 6 with the complexes [MCl] and TlTfO (1:1:1) (TfO = CF3SO3) give the cationic trinuclear complexes [M{Py(C&tbd1;CAuPTo3)2}]TfO (M = AuPTo3 (8), cis-PtCl(PPh3)2 (9)). The crystal structure of complex 6 has been determined.

Reactions of 1,12-bis(ethynyl)-1,12-dicarba-closo-dodecaborane(12), 1,12-(HC&tbd1;C)2-1,12-C2B10H10 (diethynylcarborane, decH2), with gold complexes of type [Au(acac)L] (acac = acetylacetonate) gave the neutral digold complexes [(AuL)2(μ-dec)] [L = PPh3 (1), P(C6H4OMe-4)3 (2), C(NH^tBu)(NEt2) (3)]. The neutral complex [(AuCN^tBu)2(μ-dec)] (5) was obtained by adding ^tBuNC to the complex [Au2(μ-dec)]n (4) resulting from the reaction of decH2 with [AuCl(SMe2)] and NEt3. The anionic complex PPN[Au(decH)2] (6) (PPN = Ph3P&dbd;N&dbd;PPh3) was isolated from its mixture with (PPN)2[{Au(decH)}2(μ-dec)] (7) by reacting PPN[Au(acac)2] and decH2 in 1:4 molar ratio. The rigid-rod structures of the digold compound 2·CH2Cl2 and the salt 6·CHCl3 were determined by X-ray crystallography.

The reaction of [AuCl{C(NEt2)NH^tBu}] with Tl(acac)] (1:1) gives [Au(C-acac){C(NEt2)NH^tBu}] (1). Complex 1 reacts with 2-pyridinethiol (HSpy-2), C6H4(C&tbd1;CH)2−1,3 (2:1), [Ph3PCH2CO2Me]ClO4, [Me3S(O)]ClO4, or [Me3NH]ClO4 to give, respectively, [Au(Spy-2){C(NEt2)NH^tBu}] (2), [{AuC(NEt2)NH^tBu}2(μ−C&tbd1;CC6H4C&tbd1;C-3)] (3), [Au{C(NEt2)NH^tBu}{CH(PPh3)CO2Me}]ClO4 (4), [Au{C(NEt2)NH^tBu}{CH2S(O)Me2}]ClO4 (5), or [Au{C(NEt2)NH^tBu}(NMe3)]ClO4 (6). The crystal structures of 1, 3, and 5 have been determined.

The carbonyl-stabilized phosphorus ylides Ph3P&dbd;CHCO2R (R = Me, Et) react with the platinum complexes [PtCl(η²-CH2&dbd;CH2)(N,N,N‘,N‘-tetramethylethylenediamine)]ClO4 and [PtCl2(η⁴-diene)] (diene = 1,5-hexadiene (C6H10), dicyclopentadiene (C10H12), 4-vinylcyclohex-1-ene (C8H12), norbornadiene (C7H8)) to give complexes resulting from nucleophilic attack of the ylide at one of the olefinic carbons. The crystal structures of [PtCl2{η³-C6H10CH(PPh3)CO2Et}], [PtCl2{η³-C10H12CH(PPh3)CO2Me}]·0.5CH2Cl2, and [PtCl2{η³-C8H12CH(PPh3)CO2Me}]·2CHCl3 are reported and indicate an exo attack in the case of the dicyclopentadiene complex and anti-Markovnikov addition (attack at the CH2 group) in the other two complexes.

The reactions of Q[Au(acac)2] (Q = N(PPh3)2 (PPN; a), NPr4 (b); acac = acetylacetonato) with terminal alkynes of the type HC&tbd1;CC6H4R-4 in a 1:2 molar ratio affords the complexes Q[Au(C&tbd1;CC6H4R-4)2] (R = NO2 (1), C6H4NO2-4 (2), (E)-CH&dbd;CHC6H4NO2-4 (3)). The same alkynes react with [AuCl(CNBu^t)] in NEt3 to give the complexes [Au(C&tbd1;CC6H4R-4)(CNBu^t)] (R = NO2 (4), C6H4NO2-4 (5), (E)-CH&dbd;CHC6H4NO2-4 (6)). When NHEt2 is used instead of NEt3, attack of the secondary amine at the isonitrile ligand takes place and alkynyl carbene complexes of the type [Au(C&tbd1;CC6H4R-4){C(NHBu^t)(NEt2)}] (R = NO2 (7), C6H4NO2-4 (8), (E)-CH&dbd;CHC6H4NO2-4 (9)) are obtained. The crystal structures of 1a, 4, 7, and 9 have been determined. The cubic hyperpolarizabilities of 1a,b, 4−6, 8, 9, and the related complexes [Au(C&tbd1;CC6H4R-4)(PPh3)] (R = H (10), NO2 (11), 4-C6H4NO2 (12), (E)-CH&dbd;CHC6H4NO2-4 (13), C&tbd1;CC6H4NO2-4 (14), (Z)-CH&dbd;CHC6H4NO2-4 (15), (E)-N&dbd;CHC6H4NO2-4 (16)) have been determined by Z-scans at 800 nm. An increase in γreal is observed on replacing the coligand Bu^tNC by PPh3 (proceeding from 5 to 12 and from 6 to 13), introduction of the NO2 group (proceeding from 10 to 11), extending the arylalkynyl π-bridge (proceeding from 11 to 12−15), and replacing (Z)-CH&dbd;CH by the (E)-CH&dbd;CH linking unit (proceeding from 15 to 13).

Complexes of the type PPN[Au(acac)(Ar)] [PPN = (Ph3P)2N, acac = acetylacetonate], obtained in solution from Tl(acac) and the corresponding PPN[Au(Ar)Cl] derivatives after removal of TlCl, react in situ with ethyne to give a new type of ethynylgold(I) complex, PPN[Au(Ar)(C&tbd1;CH)] [Ar = C6F5 (1), C6H4NO2-2 (2), C6H2(NO2)3-2,4,6 (3)]. The crystal structures of 1 and 3 have been determined.

[PdCl2(NCPh)2] reacts with R−carbonylmethylenethiopyridines [py{SCH2C(O)R}-2] to give, depending on the substituent R and the reaction conditions, [Pd{py{SCHC(O)Ph}-2}(μ-Cl)2Pd{py{SCH2C(O)Ph}-2}Cl] or the coordination complexes [Pd{py{SCH2C(O)R}-2}2Cl2] (R = Ph, Me, OMe). The latter can be doubly deprotonated by a base (Na2CO3 or NaH) to give dicyclometalated complexes cis-[Pd{py{SCHC(O)R}-2}2]. These transmetalate one ligand to [PdCl2(NCPh)2] to give [Pd{py{SCHC(O)R}-2}(μ-Cl)]2, which in turn reacts with (Me4N)Cl or with monodentate ligands L or with MeCN in the presence of AgClO4 to give anionic Me4N[Pd{py{SCHC(O)Ph}-2}Cl2], neutral [Pd{py{SCHC(O)R}-2}Cl(L)] [R = Ph, L = PPh3, py{SCH2C(O)Ph}-2, ^tBuNC, NH2CH(Me)Ph, pyridine (py), tetrahydrothiophene (tht); R = Me, L = PPh3, py, tht], or cationic [Pd{py{SCHC(O)R}-2}(NCMe)2]ClO4 (R = Ph, Me, OMe) complexes, respectively. The latter react with PPh3 or with bidentate ligands to give complexes [Pd{py{SCHC(O)Ph}-2}(NCMe)(PPh3)]ClO4 or [Pd{py{SCHC(O)Ph}-2}L2]ClO4 [L = PPh3, L2 = N,N,N‘,N‘-tetramethylethylenediamine (tmeda) or 2,2‘-bipyridine (bipy)]. The crystal structures of [Pd{py{SCHC(O)R}-2}2] and [Pd{py{SCHC(O)R}-2}Cl{py{SCH2C(O)R}-2}] have been determined.

Carbonyl-stabilized phosphorus ylides R3P&dbd;CHC(O)R‘ (R = Ph, Tol-p; R‘ = OEt, OMe, NMe2) react with the 1,5-cyclooctadiene complexes [MCl2(cod)] (M = Pt, Pd; cod = C8H12 = 1,5-cyclooctadiene) to give the monomeric cyclooctenyl complexes [MCl2{C8H12{CH(PR3)C(O)R‘}}]. The ylides attack in an exo fashion to give complexes which can be regarded as metalated phosphonium salts. Reactions involving the replacement of one or both chloro ligands with a neutral ligand are discussed. The crystal structures of complexes [PtCl2{C8H12{CH(PPh3)CO2Me}}] and [Pt{C8H12{CH(PPh3)CO2Me}}(py)2](CF3SO3)2 are reported.

Na[AuCl4] reacts with [py{SCH2C(O)R}-2] (py-2 = 2-pyridyl) at room temperature to give cyclometalated alkylgold(III) complexes [AuCl2{py{SCHC(O)R}-2}] [R = Ph (1a), Me (1b), OMe (1b)], which in turn react with NaBr or with PR‘3 in the presence of NaClO4 to give [AuBr2{py{SCHC(O)R}-2}] [R = Ph (2a), Me (2b)] or a mixture of SP4-3- and SP4-4-[AuCl{py{SCHC(O)R}-2}(PPh3)]ClO4 [R = Ph (3a), Me (3b)]. This mixture of isomers converted to the isomer SP4-4 upon refluxing in chloroform. When the last reaction was made using P(C6H4OMe-4)3, the main products were [AuCl{P(C6H4OMe-4)3}] and [Hpy{SCH2C(O)Ph}-2]ClO4. The crystal structure of the latter has been determined.

Complexes [MCl2L2] (M = Pd, Pt; L2 = 2,2‘-bipyridine (bpy) or Me2N(CH2)2NMe2 (tmeda)) react with ketones MeC(O)R (R = Me, Et) in the presence of bases (Ag2O or M‘OH (M‘ = Na, K)) to give the new types of ketonyl palladium(II) and platinum(II) complexes [M{CH2C(O)R}ClL2] (M = Pd, L2 = N,N,N‘,N‘-tetramethylethylenediamine = tmeda; M = Pt, L2 = 2,2‘-bipyridine = bpy) and [Pt{CH2C(O)R}2L2] (R = Me, Et, L2 = bpy). Oxidative addition of chloroacetone on [Pt(dba)2] in the presence of bpy also yields [Pt{CH2C(O)R}ClL2]. [Pd{CH2C(O)Me}Cl(tmeda)] reacts with PhNHNH2 in the presence of TlOTf (OTf = CF3SO3) to give the cyclometalated complex [Pd{CH2C(Me)&dbd;NNH(Ph)}(tmeda)]OTf. The crystal structure of [Pt{CH2C(O)Me}2(bpy)] has been determined. The platinum atom is in a distorted square-planar environment. The strong trans influence of the acetonyl ligand promotes the lengthening of both Pt−N bonds (2.082(3) and 2.091(3) Å) with concomitant narrowing of the NPtN bond angle (78.89(13)°).

[(PPh3)2N][Au(acac)2] (acac = acetylacetonate) reacts with terminal alkynes RC&tbd1;CH to give [(PPh3)2N][Au(C&tbd1;CR)2] (R = H, ^tBu, SiMe3, CH2X (X = Cl, Br, OH)) complexes. The reactions between [(PPh3)2N][Au(C&tbd1;CH)2] and [(PPh3)2N][AuX2] (X = Cl, Br, I) give [(PPh3)2N][Au(C&tbd1;CH)X] complexes. Neutral mononuclear [Au(C&tbd1;CR)(NHEt2)] (R = SiMe3, ^tBu), [Au(C&tbd1;CR)(PR‘3)] (R = H, R‘ = Ph, C6H4OMe-4; R = CH2Cl, CH2Br, CH2OH, R‘ = Cy = cyclohexyl; R = SiMe3, R‘ = Ph, C6H4OMe-4, Cy; R = ^tBu, R‘ = Ph, Cy, C6H4OMe-4), [Au(C&tbd1;CR)(CN^tBu)] (R = SiMe3, ^tBu), and [Au(C&tbd1;CR){C(NH^tBu)(NEt2)}] (R = H, SiMe3, ^tBu) or dinuclear [(AuL)2{μ-C&tbd1;C(CH2)5C&tbd1;C}] (L = PPh3, CN^tBu, C(NH^tBu)(NEt2)) are obtained via a variety of synthetic methods:  (i) reaction between [(PPh3)2N][Au(C&tbd1;CH)2] and [Au(PR3)2]ClO4, (ii) reaction of terminal alkynes with [Au(acac)(L)], (iii) reaction of [AuClL] complexes with terminal alkynes in diethylamine, (iv) substitution reactions (e.g., [Au(C&tbd1;CR)(NHEt2)] + PR‘3), (v) reaction of diethylamine with alkynyl isocyanide derivatives to give alkynylcarbene complexes. The crystal structures of [(PPh3)2N][Au(C&tbd1;CCH2OH)2], [Au(C&tbd1;CSiMe3)(CN^tBu)], and [Au(C&tbd1;CR)(PR‘3)] (R‘ = Cy, R = CH2Cl, CH2Br; R‘ = Ph, R = SiMe3, ^tBu) were determined.

Complexes Q[Au(R)Cl] react with H2S in the presence of diethylamine to give the corresponding organo(hydrosulfido)gold(I) complexes Q[Au(R)(SH)] [R = C6F5, Q = Ph3P&dbd;N&dbd;PPh3 = PNP, Bu4N; Q = PNP, R = C6H4NO2-2, C6H2(NO2)3-2,4,6]. Under the same reaction conditions, Me4N[Au(C6F5)Cl] gives the bridging organo(μ3-sulfido)gold(I) complex (Me4N)2[{Au(C6F5)}3(μ3-S)], whereas Et4N[Au(C6F5)Cl] gives Et4N[Au(C6F5)SH] or (Et4N)2[{Au(C6F5)}3(μ3-S)] depending on the workup procedure. The crystal structure of Et4N[{Au(C6F5)}3(μ3-S)]·0.5MeC(O)Et has been determined. The Au···Au contacts are 3.1844, 3.2773, and 3.4772 Å, with corresponding angles 86.68, 90.31, and 97.65° at sulfur.

The intramolecular aldol-like condensation of two acetimino ligands has been observed for the first time to occur in [Rh(Cp*)Cl(NH&dbd;CMe2)2]ClO4 (1·ClO4), under catalytic or stoichiometric reaction conditions, to give [Rh(Cp*)Cl{N,N-NH&dbd;C(Me)CH2C(Me)2NH2}]X (2·X, X = Cl, ClO4). The crystal structures of 1·ClO4 and 2·Cl have been determined.