J. P. Jun. Fackler

Dimethylgold(III) complexes. Synthesis of several compounds with AuC2S2 coordination. The crystal and molecular structure of [(CH3)2AuSC2H5]2

Abstract The synthesis and characterization of several new dimethylgold(III) complexes are reported along with the X-ray crystal structure of [(CH 3 2 AuSC 2 H 5 ] 2 . The latter compound crystallizes in a triclinic space group P 1 , a = 6.193(1) A, b = 7.852(1) A, c = 14.614(3) A, α = 92.36(1)°, β = 93.99(2)°, γ = 92.19(1)°, Z = 2 with V = 707.88(23) A 3 . This dimer shows a syn -endo Au 2 (SR) 2 rhombus with a 141.3° dihedral angle. Refinement gave R = 0.078 with a Au⋯Au distance of 3.457(3) A. General procedures are reported for the synthesis of dithioate complexes of (CH 3 ) 2 Au III . New compounds are reported are: (CH 3 ) 2 AuS 2 P(CH 3 ) 2 ; (CH 3 ) 2 AuS 2 P(OC 2 H 5 ) 2 ; (CH 3 ) 2 AuS 2 P(C 6 H 5 )(OC 2 H 5 ); (CH 3 ) 2 Au[CH 3 C(S)CH(S)OC 2 H 5 ]; (CH 3 ) 2 AuS 2 COC 2 H 5 ; (CH 3 ) 2 AuS 2 CC 6 H 5 ; (CH 3 ) 2 Au[(CH 3 ) 2 P(S)NP(S)(CH 3 ) 2 ]; [(C 2 H 5 ) 4 N][(CH 3 ) 2 AuS 2 C 2 (CN) 2 ].

Structure of [3,5-(C6H5)2C3H2N2]4. A 3,5-diphenylpyrazole tetramer linked by hydrogen bonds

3,5-Diphenylpyrazole, C 15 H 12 N 2 , M r =220.1, monoclinic, C2/c (No. 15), a=16.948 (4) A, b=17.163 (4) A, c=17.677 (6) A, β=109.59 (2) o . V=4844 (2) A 3 , Z=32, D x =1.21 Mg m -3 . λ(Mo Kα)=0.71069 A, μ=0.07 mm -1 , F(000)=1861.6, T=298 K, final R=0.056 and wR=0.058 for 259 variable parameters and 2073 reflections with F 0 2 >3σ(F 0 2 ). The asymmetric unit consists of a hydrogen-bonded dimer of 3,5-diphenylpyrazole which is further hydrogen bonded to form four discrete tetrameric aggregates per unit cell

Luminescent Tris(3-ethyl-1,5-diaza-3-azonia-7-phosphatricyclo[3.3.1.13,7]decane-P)gold(I) Tetraiodide Trihydrate, [(EtTPA)3Au]I4.3H2O

The title complex, [Au(C8H17N3P)3]I4.3H2O, has the complex cation lying with its Au and associated I atom on a crystallographic threefold axis. The AuP3 moiety has distorted trigonal-planar geometry [the Au atom is 0.336 (3) A from the P3 plane], with Au—P 2.334 (3), Au⋯I 2.9129 (12) A and P—Au—P 117.97 (3)°. The asymmetric unit also has one iodide ion and one water molecule in general positions, with O⋯I distances [3.516 (2) and 3.576 (2) A] consistent with O—H⋯I hydrogen bonding.

Benzenethiolato(triphenylphosphine)gold(I)

The crystal structure of [Au(C 6 H 5 S)(C 18 H 15 P)] contains two Au I centers; each Au I is almost linearly coordinated [P-Au-S bond angles of 179.0 (1) and 175.9 (1) o ] and an Au I ...Au I intramolecular distance of 3.154 (2) A is found

Two crystalline polymorphs of chloro[tris(2‐cyanoethyl)phosphine]gold(I), [AuCl(C9H12N3P)]

Polymorph (1) has Au-Cl and Au-P bond lengths of 2.295 (3) and 2.225 (3) A, respectively, with a P-Au-Cl bond angle of 177.8 (1) o . Polymorph (2) has Au-Cl and Au-P bond lengths of 2.315 (2) and 2.243 (2) A, respectively, with a P-Au-Cl bond angle of 177.1 (1) o . Polymorph (2) crystallizes with two of the C≡N groups alongside the Au I center in the asymmetric unit

The reactivity of bromoform with [Au(CH2)2PPh2]2. The completion of the halomethane series CHyX4−y (y=3,2,1,0; X=Cl, Br, I) and reactivity with [Au(CH2)2PPh2]2

The reaction of [Au(CH2)2PPh2]2 with excess CHBr3 in benzene initially gives [Au(CH2)2PPh2]2− (CHBr2)Br. This observation establishes that halomethanes, CHyX4−y (y=3,2,1,0; X=Cl, Br, I), react with [Au(CH2)2PPh2]2 to initially give Au(II) adducts of the general form [Au(CH2)2PPh2]2−(CHyX3−y)X (y=3,2,1,0) via oxidative addition across the carbon-halogen bond. The order of reactivity inversely follows the order of carbon-halogen bond dissociation energies of haloalkanes. Methyl chloride is the only halomethane of the series that does not give a Au(II) adduct under similar reaction conditions.

Structure of trichloro(triphenylphosphine)gold(III), [AuCl3{P(C6H5)3}]

The structure of the title compound displays the same trans effects and slight distortions from planarity as previously reported trihalide(trialkylphosphine)gold(III) structures

Bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato-S,S')gold(III), [Au{P(C2H5)3}2][Au(S2C6H4)2]

The structure of the title compound consists of [Au(PEt 3 ) 2 ] + cation and [Au(S 2 C 6 H 4 ) 2 ] − anion pairs. The gold(I) cations exhibit linear coordination to two PEt 3 ligands. The geometry of the gold(III) anions is square planar with four S atoms coordinated to the Au center. Typical Au-S and Au-P distances are observed

(o-Methoxybenzenethiolato)(triphenylphosphine)gold(I) diethyl ether solvate

The crystal structure of [Au(C 7 H 7 OS)(C 18 H 15 P)]. 0.25C 4 H 10 O contains two Au I centers; each Au I is almost linearly coordinated [P-Au-S bond angles of 175.2(1) and 176.2(1) o ] and a large Au I ...Au I intramolecular distance of 5.741 (3) A is found

Bis(tri-n-butylphosphino)gold(I) tetraphenylborate

The Au atom is linearly coordinated to two disordered tri-n-butylphosphine ligands with Au-P distances of 2.310 (3) and 2.305 (4) A and a P-Au-P bond angle of 176.1 (1) o