Paul A. Tucker

The crystal structure of tetrabutylammonium trichlorocarbonylplatinate(II)

Abstract Crystals of [C 16 H 36 N] + [Cl 3 COPt] − are monoclinic, space group P 2 1 / n , with a 14.949(8), b 8.892(7), c 18.232(10) A, β 105.5(3)°, Z 4. The structure has been refined by least-squares to a final R of 0.042 for 2358 counter intensities. The PtCl bond lengths in the square-planar anion are not significantly different (mean value 2.291 A) and the PtC (carbonyl) bond length is 1.82 A. Conclusions are drawn on the factors affecting the trans influence in this complex and a number of related square planar Pt II chloro-complexes.

Addition of hexafluoro-2-butyne to palladium(II) β-diketonato rings: The crystal structure of the adduct Pd (Acac)2(C4F62

Abstract A crystal structure analysis shows that hexafluoro-2-butyne reacts with bis(acetylacetonato)palladium(II) to give Pd[OC(Me)CH(COMe)C(CF3)C(CF3)]2 in which the hexafluoro-2-butyne links the γ-CH of the β-diketonato ligands to the palladium. Other palladium(II)β-diketonato systems behave similarly.

The crystal and molecular structure of μ-μ-dichlorobis(hexafluorobut-2-enyl)-bis(cycloocta-1,5-dienyl)diiridium(III).

Abstract The title compound is isolated from reaction of hexafluorobut-2-yne with μ-μ-Dichlorobis(cycloocta-1,5-diene)diiridium(I) at 90°C. Crystals of the complex, solvated with deuterobenzene, are monoclinic, space group P 21/ n with a = 10.97 + 0.02, b = 17.96 + 0.03, c = 11.63 + 0.02 », β = 127.4 + 0.60°. The acetylene has abstracted a hydrogen atom forming a σ-bonded cis -vinylic group and the original cyclooctadiene, having lost a proton, is coordinated as the cycloocta-1,5-dienyl ligand. Mean bond lengths are IrCl 2.467, IrC (allylic) 2.17, IC (olefinic) 2.36 and IrC (vinylic) 2.09 ».

1,4-Addition of hexafluorobut-2-yne to co-ordinated cyclo-octa-1,5-diene: crystal and molecular structure of (acetylacetonato)aqua{7–8-η-7,8-bis(trifluoromethyl)bicyclo[4.2.2]dec-7-ene-2,5-diyl}rhodium(III)

Crystals of the title compound (1) are monoclinic, space group C2/c, with a= 8.84(1), b= 19.34(2), c= 22.61(2)A, β= 102.8(5)°, Z= 8. The structure was refined by least-squares analysis of counter intensities to R 0.092 for 1 591 reflexions. Mean bond lengths are: Rh–C 2.05, Rh–C(olefinic) 2.09, Rh–O(trans to C) 2.05, Rh–O(trans to olefinic bond) 2.18, and Rh–OH2 2.32A. Possible intermediates to the formation of the adduct are discussed.

1,4 Addition of hexafluorobut-2-yne to co-ordinated cyclo-octa-1,5-diene: crystal structures of the adducts [Rh(acetylacetonato)(C8H12)(C4F6)(1½H2O)] and [Ir(acetylacetonato)(C8H12)(C4F6)2]

Hexafluorobut-2-yne adds 1,4 to co-ordinated cyclo-octa-1,5-diene in the complex [Rh(cod)Cl]2, in contrast to the reaction of hexafluorobut-2-yne with [Ir(acac)(cod)] which gives an iridiacyclopentene ring system.

Side-bonded ketone complexes of platinum(0). Indan-1,2,3-trione complexes; molecular and crystal structure of [2,2′,-bis(indan-1,2,3-trionato)(2–)-O2O2′]bis(triphenylphosphine)platinum

Reactions of equimolar quantities of [PtL4](L = PPh3 or AsPh3) with either indan-1,2,3-trione (int) or 2,2-di-hydroxyindan-1,3-dione afford the side-bonded ketone complexes [Pt(int)L2] which undergo ring-expansion reactions with int to give [Pt{(int)2}L2]. Crystals of the adduct [Pt{(int)2}(PPh3)2] are monoclinic, space group Cc with a= 22.08, b= 14.47, c= 30.72 A, β= 95.1°, and Z= 8. Least-squares refinement of the structural parameters reduced R to 0.078 for 2 382 reflections. The adduct has the two indan-1,2,3-trione moieties linked via the carbon atoms of the central carbonyl groups and bonded by the oxygen atoms at these groups to the platinum to give a five-membered 1,3-dioxa-2-platinolan ring. Ring-expansion reactions of [Pt(int)L2] and ring-substitution reactions of [Pt{(int)2}L2], with hexafluoropropan-2-one and hexafluorobut-2-yne are also described. Reactions with hexafluoropropan-2-one give both five- and seven-membered ring systems. The side-bonded complexes [Pt(int)L2] react with dioxygen to give cyclic dicarboxylato-complexes.

The reaction of hexafluorobut-2-yne with [Rh(Me3CCOCHCOCCMe3)(CO)2]: The x-ray crystal structure of a complex containing an alkyne co-ordinated parallel to a rhodium-rhodium bond

Abstract Hexafluorobut-2-yne reacts with [Rh(dpm)(CO) 2 ], (dpm = dipivaloylmethanato) to give the complex, [Rh 2 (dpm.C 4 F 6 ) 2 (C 4 F 6 )(CO) 2 ], in which there is an alkyne molecule co-ordinated parallel to a rhodium-rhodium bond. Crystals of the complex, [Rh 2 (dpm.C 4 F 6 ) 2 (C 4 F 6 ) (CO) 2 ] are triclinic, space group P T with a = 15.34, b = 18.50, c = 16.01A, α = 83.9, β = 99.2, = 89.5, z = 4. The alkyne bridges the metal atoms to give a dirhodacyclobutene ring, the carbon-carbon bond is inclined by 15° to the rhodium-rhodium bond. Mean bond lengths are RhRh 2.684, RhO 2.30, 2.19 and ???.10, RhC(carbonyl) 1.78 and RhC (CF 3 )C(CF 3 ) 2.11A. The η 4 -hexakistrifluoromethylbenzene complex, [Rh(dpm.C 4 F 6 ){C 6 (CF 3 ) 6 }] is formed from C 4 F 6 and [Rh(dpm)(CO) 2 ] at 110°C. The reactions described show similarities to the reaction of hexafluorobut-2-yne with [RhCp(CO) 2 ], (cp=η 5 -C 5 H 5 ).

An alkene—alkyne metal complex: the preparation and crystal structure of chloro(cycloocta-1,5-diene)(hexafluorobut-2-yne)iridium(I) dimer and chloro(cycloocta-1,5-dienyl)(hexafluorobut-2-enyl)iridium(III) dimer

Abstract Hexafluorobut-2-yne reacts with chloro(cycloocta-1,5-diene)iridium(I) dimer at 20 °C to give a complex [IrCl(cod)(C4F6)]2 in which both the diene and the acetylene are π-coordinated to the same iridium atom; an isomeric product, [IrCl(CCF3CHCF3)(C8H11)]2, is isolated from the same reactants at 90 °C.

Crystal structures of hydrido-, fluoro-, and chloro-tris(triethyl-phosphine)platinum(II) salts

Crystals of [Pt(PEt3)3H][PF6] are triclinic, P, with a= 15.969(3), b= 20.600(3), c= 9.081 (2)A, α= 79.87(2), β= 88.91(2), γ= 82.49(2)°, and Z= 4. Crystals of [Pt(PEt3)3F][BF4] are monoclinic, P21/c with a= 15.627(13), b= 10.988(8), c= 16.347(16)A, β= 102.7(3)°, and Z= 4. Crystals of [Pt(PEt3)3Cl][BF4] are monoclinic. P21/n, with a= 11.507(11), b= 17.452(18), c= 14.199(20)A, β= 104.6(4)°, and Z= 4. Least-squares refinements for these three complexes converged with R= 0.049 (4 485 reflections), R 0.045 (3 008), and 0.047 (3 634) respectively. Mean bond lengths are Pt–P(trans to H) 2.335(4), Pt–P(cis to H) 2.300(3), Pt–P (trans to F) 2.239(3), Pt–P (cis to F) 2.337(4), Pt–P (trans to Cl) 2.251(3), Pt–P (cis to Cl) 2.353(3), Pt–F 2.043(7), and Pt–Cl 2.366(3)A. The Pt–P bond lengths trans to the anionic ligand (X) in the cations follow the expected trans-influence order, whereas those cis to X follow the order Pt–P (cis to Cl) > Pt–P (cis to F) > Pt–P (cis to H) which reflects the anionic size of X.

Crystal and molecular structure of cis-chloro(3-chloro-1,1,3,3-tetrafluoropropan-2-one)bis(triphenylphosphine)platinum(II)

Crystals of the title compound are monoclinic, space group P21/a, with a= 20.45 ± 0.02, b= 1 8.66 ± 0.02, c= 10.43 ± 0.01 A, β= 114.0 ± 0.4°. The structure was solved by conventional Patterson and Fourier techniques and refined by block-diagonal least-squares analysis of counter intensities to R 0.095 for 3 956 reflections. Important bond lengths are Pt–P (trans to C) 2.362(5), Pt–P (trans to Cl) 2.247(5), Pt–Cl 2.349(6), and Pt–C 2.06(2)A.