Jennifer M. Patrick

Cluster chemistry: LVI. Stereochemistry of group 15 ligand-substituted derivatives of M3(CO)12 (M = Ru, Os) B. X-Ray structures of six complexes M3(CO)10(L)2 (M = Ru, L = PPh3, PPh(OMe)2, and P(OCH2CF3)3; M = Os, L = PPh3, PPh(OMe)2 and P(OMe)3)

Abstract X-Ray crystal structures of six complexes of the type M 3 (CO) 10 (L) 2 (M = Ru, L = PPh 3 , PPh(OMe) 2 , and P(OCH 2 CF 3 3 ; M = Os, L = PPh 3 , PPh(OMe) 2 and P(OMe) 3 ) have been determined. All contain a triangular M 3 core; the two phosphorus ligands occupy equatorial positions on adjacent metal atoms so that they are approximately trans to each other at the ends of the M-M vector. In contrast to complexes M 3 (CO) 11 (L), there is no prounounced lengthening of the MM bonds cis to the group 15 ligand. Other features, including twisting of the ML 4 groups to distort the D 3h symmetry towards D 3 , are similar to those found for monosubstituted complexes. Thermal reactions between Os 3 (CO) 12) and P(OMe) 3 , which afford Os 3 (CO) 12- n {P(OMe) 3 } n ( n = 1–4), are described. Crystal data: Ru 3 (CO) 10 (PPh 3 ) 2 : orthorhombic, P 2 1 2 1 2 1 , τa 34.636(15), b 17.007(10)(10), c 14.806(4) A, U 8721(7) A 3 , Z = 8, N 0 (number of ‘observed’ data with I > 3σ( I ) = 4773, R = 0.071, R ′ = 0.080; Os 3 (CO) 10 (PPh 3 2 : monoclinic, P 2 1 / n , a 17.104(6), b 34.507(11), c 14.832(6) A, β 92.28(3)°, U 8747(5) A 3 Z = 8, N 0 = 8011, R = 0.048, R ′ = 0.040; Ru 3 (CO) 10 {PPh(OMe) 2 } 2 : monoclinic, Pc, a 9.014(4), b 8.545(4), c 21.728(5) A, β 100.77(3)°, U 1644(1) A 3 , Z = 2, N 0 = 5269, R = 0.024, R ′ = 0.027; Os 3 (CO) 10 {PPh(OMe) 2 } 2 : monoclinic, Pc, a 9.007(5), b 8.565(7), c 21.716(12) A, β 100.87(5)°, U 1645(1) A 3 , Z = 2, N 0 = 5266, R = 0.041, R ′ = 0.043; Ru 3 (CO) 10 {P(OCH 2 CF 3 ) 3 } 2 : orthorhombic, P 2 1 2 1 2 1 , a 29.79(2), b 15.827(8), c 8.283(4) A, U 3906(3) A 3 , Z = 4, N 0 = 2652, R = 0.063, R ′ = 0.070; Os 3 (CO) 10 {P(OMe) 3 } 2 : triclinic, P 1 , a 24.955(10), b 9.439(4), c 8.944(4), A, a 84.02(3), β (3), γ 84.18(3)°, U 2083(1) A 3 , Z = 3, N 0 = 40.84, R = 0.057, R ′ = 0.068.

Cluster chemistry. Part 45. Synthesis and some reactions of [Ru3(µ3-PPhCH2PPh2)(CO)9]– : X-ray crystal structures of [MRu3(µ3-PPhCH2PPh2)(CO)9(PPh3)](M = Cu, Ag, or Au)

Reactions between K[BHBus3] and [Ru3(CO)10(µ-EPh2CH2EPh2)](E = P or As) afford solutions of the dephenylated anions, [Ru3(µ3-EPhCH2EPh2)(CO)9]–, which can be reversibly protonated to give [Ru3(µ-H)(µ3-EPhCH2EPh2)(CO)9]. The latter complexes may also be obtained directly from [Ru3(CO)10(µ-EPh2CH2EPh2)] and H2(20 atm, 80 °C, 2h) in cyclohexane (yields 65–75%). Similar complexes were obtained in poor yield from [Ru3(CO)10(µ-PPh2CH2CH2PPh2)]. The group 1 B metal-containing clusters [MRu3(µ3-EPhCH2EPh2)(CO)9(PPh3)](E = P, M = Cu, Ag, or Au; E = As, M = Au) were prepared from [Ru3(µ3-EPhCH2EPh2)(CO)9]– and sources of [M(PPh3)]+; the analogous [AuRu3(µ3-PPhCH2CH2PPh2)(CO)9(PPh3)] was also obtained. Single-crystal X-ray studies on the first three, title complexes showed that they are isostructural, the M(PPh3) fragment bridging the same Ru–Ru bond as that bridged by the PPh group of the face-capping phosphidophosphine ligand. Detailed examination of bond parameters in the Ru2MP moiety suggests that the three M(PPh3) fragments are not strictly isolobal, although it is the Ag(PPh3) fragment which interacts least strongly with the Ru3 core. The structures were refined by least-squares methods to residuals of 0.039, 0.044, and 0.041 for 4 560, 4 917, and 9 275 independent ‘observed’ reflections, respectively.

Cluster chemistry. XXXXIV: X-ray structures of [Ru3(CO)11(CNBut)] (at 130 K) and [Os3(CO)11(CNBut)] (at 295 K)

Abstract Single crystal X-ray structure determinations are reported for [Os3(CO)11(CNBut)] at 295 K and for [Ru3(CO)11(CNBut)] at ∼ 130 K; both structures are isomorphous with the previously determined room-temperature structure for the latter, which exhibited ∼ 14% disorder in the Ru3 core. Residuals for the present studies were 0.042 and 0.033 for 4491 and 6072 observed reflections respectively. The osmium complex is fully ordered; disorder in the ruthenium complex is reduced to ∼ 6% at low temperature, indicating the disorder to be dynamic rather than a consequence of packing error.

Cluster chemistry. Part 32. Synthesis and X-ray crystal structure of [Ru5(µ5-η2-C2PPh2-P)(µ-PPh2)(CO)13], a complex containing an alkynyl ligand in extended interaction with an open Ru5 cluster

The radical ion-initiated reaction between [Ru3(CO)12] and C2(PPh2)2(dppa)(in 2 : 1 ratio) gives [{Ru3(Co)11}2(µ-dppa)](2), in which the acetylenic bis-tertiary phosphine bridges two monosubstituted Ru3 clusters. On heating (90 °C, 1 h), complex (2) is converted into [Ru5(µ5-η2-C2PPh2-P)(µ-PPh2)(CO)13](3) in 88% yield, which was characterised by an X-ray study at 295 K. The complex contains a seven-electron donor C2PPh2 ligand interacting with all five Ru atoms of an open Ru5 cluster consisting of three edge-fused Ru3 triangles (a ‘swallow’ cluster); the PPh2 group bridges the non-fused edge of the central triangle. Some comparisons with [Ru5(µ5-CNBut)(CO)14(CNBut)] and [Ru5(µ5-C2Ph)(µ-PPh2)(CO)14] are made. Crystals of complex (3) are monoclinic, space group P21/n, with a= 17.00(1), b= 17.394(9), c= 14.260(7)A, β= 92.89(4)°, and Z= 4; the structure was refined by least-squares methods to a residual of 0.031 for 6 364 independent ‘observed’ reflections.

Cluster chemistry. Part 18. Isocyanide complexes derived from [Ru3(CO)12]: crystal and molecular structures of [Ru3(CO)12 –n(CNBut)n](n= 1 or 2)

Reactions between [Ru3(CO)12] and isocyanides CNR have given the complexes [Ru3(CO)12 –n(CNR)n](R = But, n= 1, 2, or 3; R = C6H11, n= 1; R = C6H4OMe-p, n= 1 or 2; and R = CH2SO2C6H4Me-p, n= 3) as orange to red crystalline solids. The crystal structures of [Ru3(CO)12 –n(CNBut)n](n= 1 or 2) have been determined by X-ray diffraction studies, and refined to residuals of 0.035 (4 561 ‘observed’ reflections) and 0.043 (2 849 ‘observed’ reflections) respectively. Crystals of [Ru3(CO)11(CNBut)] are monoclinic, space group P21/c with a= 11.948(5), b= 12.108(4), c= 16.621(4)A, β= 112.74(2)°, and Z= 4; crystals of [Ru3(CO)10(CNBut)2] are monoclinic, space group P21/a with a= 11.910(10), b= 12.831(17), c= 9.565(16)A, β= 111.84(10)°, and Z= 2. In the latter derivative, the ligand array is ‘centrosymmetric’ about a crystallographic special position, with the two isocyanide ligands in axial sites; the Ru3 triangle is disposed about a pair of equally populated centrosymmetrically related dispositions within the ligand array. In [Ru3(CO)11(CNBut)] the isocyanide substituent is also axial; the Ru3 triangle is similarly disordered but only to the extent of ca. 14% within the ligand array. A method for the almost quantitative conversion of RuCl3·xH2O to [Ru3(CO)12] has been developed consisting of carbonylation of 1% methanol solutions (50–60 atm CO, 125 °C, 16–18 h), recycling the mother-liquors with fresh RuCl3·xH2O.

Cluster chemistry XXIV. X-ray structure of H4 Ru4(CO)9(PMe2 Ph)[P(OC6H4 Me-p)3]-[P(OCH2)3CEt], a chiral cluster complex containing four different ligands

Abstract The X-ray structure of H4Ru4(CO)9(PMe2Ph)[P(OC6H4Me-p)3][P(OCH2)3CEt], a chiral cluster complex, has been determined. The complex is triclinic, space group P 1 , a 19.812(7), b 14.299(4), c 10.323(4) A, α 100.09(3), β 98.18(3), γ 102.23(3)°. The unit cell contains an enantiomeric pair of molecules. The Ru4 core contains two short (av. 2.785 A) and four long (2.967 A) RuRu separations with approximate D2d symmetry. RuP separations are 2.254(6) A [to P(OCH2)3CEt], 2.270(6) A [to P(OC6H4Me-p)3] and 2.326(7) A [to PMe2Ph]; all P-donor ligands are trans to short RuRu vectors.

Lewis-base adducts of lead(II) compounds. Part 4. Novel isomeric dimers of lead(II) thiocyanate–1 10-phenanthroline(1/2). Crystal structure determinations

The 1 : 2 adduct of lead(II) thiocyanate–1,10-phenanthroline has been shown to crystallise as two distinct polymorphs, monoclinic and triclinic. Single-crystal X-ray structure determinations show that in both forms the complexes exist as discrete dimers, all lead environments being seven-co-ordinate. The lead environment in all cases comprises a pair of bidentate phenanthroline ligands, unidentate N-thiocyanate, and a pair of bridging thiocyanate ligands, one with bridging sulphur and one bridging through the terminal atoms. In the monoclinic form C2/c, the dimer has crystallographically imposed two-fold symmetry with the N,S-bridging thiocyanate disordered about that axis; this ligand in the triclinic form is fully ordered, with ligand rearrangement about one of the lead atoms so that the dimer symmetry is more nearly inversion rather than two-fold.

Co-ordination chemistry of pyridyl and N-methylimidazolyl ketones. Synthetic and X-ray structural studies of copper(II), nickel(II), and dimethylgold(III) complexes

Di-2-pyridyl ketone (dpk) reacts with dimethylgold(III) nitrate in water to form the complex [AuMe2(dpk·H2O)]NO3 in which the ligand has been hydrated to form a geminal diol. The closely related ketones 2-pyridyl N-methyl-2-imidazolyl ketone (pik) and di(N-methyl-2-imidazolyl) ketone (dik) react with AuIIIMe2 nitrate to form complexes that do not involve hydration of the ligand, [AuMe2(L)]NO3(L = pik or dik). They react similarly with copper(II) sulphate and nickel(II) nitrate, forming [Cu(pik)(SO4)]·O.5H2O, [Cu(dik)(SO4)]·2H2O [Ni(pik)2(NO3)2]·0.5H2O, and [Ni(dik)2(NO3)2]·1.5MeOH; dpk forms [Ni(dpk·H2O)2(NO3)2]·0.5H2O on reaction with nickel(II) nitrate. The crystal structures of [AuMe2(dpk·H2O)] NO3 and [Cu(dik)(SO4)]·2H2O have been determined by single-crystal X-ray diffraction at 295 K and refined by least-squares methods to R= 0.045 and 0.032 for 2 031 and 4 754 independent ‘observed’ reflections, respectively. The cation [AuMe2(dpk·H2O)]+ has the ligand N,N-chelated with cis-square-planar co-ordination for gold(III), with an intramolecular hydroxy group positioned 2.850(8)A from the gold atom. The complex [Cu(dik)(SO4)]·2H2O has square-pyramidal co-ordination for copper(II), with the N,N-chelated ligand in the basal plane together with a water molecule and unidentate sulphate ion, and a water molecule co-ordinated axially. There is an intermolecular Cu ⋯ O contact of 3.254(2)A with a ketone oxygen. Possible reasons for different behaviour of the ligands toward hydration are discussed. Crystals of [AuMe2(dpk·H2O)] NO3 are monoclinic, space group P21/c, a= 9.41 (1), b= 7.328(7), c= 22.17(2)A, β= 97.85(8)°, and Z= 4. Crystals of [Cu(dik)(SO4)]·2H2O are monoclinic, space group P21/n,a= 11.982(3), b= 13.803(3), c= 8.866(2)A, A= 107.30(2)°, and z= 4.

Rapid intramolecular interactions between organic isocyanates and hexafluorobut-2-yne on a dirhodium centre; X-ray crystal structure of (η-C5H5)2Rh2 {μ2(η3-C(CF3)C(CF3)C(O)N(Ph)}

Abstract Complexes of formula (η-C 5 H 5 2 Rh 2 {CF 3 C 2 CF 3 · RNCO} have been prepared by three methods, from reactions between organic isocyanates and (η-C 5 H 5 ) 2 Rh 2 (CO)(CF 3 C 2 CF 3 ) or (η-C 5 H 5 ) 2 Rh 2 (CO) 2 (CF 3 C 2 CF 3 ); by treatment of (η-C 5 H 5 ) 2 Rh 2 (CO)(CF 3 C 2 CF 3 ) with organic azides; and by oxidation with Me 3 NO of the organic isocyanide in (η-C 5 H 5 ) 2 Rh 2 (CO)(CNR)(CF 3 C 2 CF 3 ). The crystal and molecular structure of the complex (η-C 5 H 5 ) 2 Rh 2 {CF 3 C 2 CF 3 · RNCO} with R = Ph has been determined from single crystal X-ray diffraction data. This reveals that the isocyanate has condensed with the hexafluorobut-2-yne to form an amide ligand of the form C(CF 3 )C(CF 3 )C(=O)N(R); this bridges the two rhodium atoms in a μ 2 η 3 -manner.

Structure and stereochemistry in f-block complexes of high co-ordination number. Part 3. The [M(bidentate ligand)2(unidentate ligand)4] system : crystal structures of tetrakis(isothiocyanato)bis(octamethylpyrophosphoramide-OO″)uranium(IV) and tetrachlorobis(octamethylpyrophosphoramide-OO″)thorium(IV)

The crystal structures of octamethylpyrophosphoramide (ompp) adducts of uranium(IV) thiocyanate and thorium(IV) chloride have been determined and the complexes shown to be [U(NCS)4(ompp)2](1) and [ThCl4(ompp)2](2). The structures were refined by least squares to residuals of 0.043 [(1), 2 926 ‘observed’ reflections] and 0.060 [(2), 2 209 ‘observed’ reflections] for X-ray diffraction data measured at 295 K. For (1), crystals are orthorhombic, space group Fdd2, with unit-cell dimensions a= 44.26(2), b= 20.69(1), c= 9.110(5)A, and Z= 8; for (2), crystals are monoclinic, space group P21/n, with unit-cell dimensions a= 18.714(7), b= 10.883(3), c= 18.999(7)A, R = 105.01(3)°, and Z= 4. In each case the metal atom is eight-co-ordinated by the four unidentate ligands and a pair of bidentate octamethylpyrophosphoramide ligands. In (1) the metal atom lies on a crystallographic two-fold axis; U–N are 2.423(9) and 2.466(10)A and U–0 2.297(6) and 2.414(7)A. In (2) the molecule has no crystallographically imposed symmetry and Th-O range between 2.412(16) and 2.455(16)A and Th-CI between 2.725(8) and 2.763(7)A. The two compounds are two different structural isomers of the system [M(bidentate ligand)2(unidentate ligand)4]. The stereochemistry about the metal atom in (1) is square antiprismatic, whereas in (2) it is dodecahedral.