Crystal Structure Of Fac Research Articles

Stabilization of zero-valent hydrazido complexes by phosphine ligands. Crystal structure of fac-(CO)3(DPPE)W:NNMe2, a nitrene analogue to Fischer carbenes

The zero-valent tungsten hydrazido complex (CO) 5 W=NNMe 2 (2) reacts with phosphines or phosphites to form cis-(CO) n (PR 3 ) 5-n W=NNMe 2 (3, 8, and 10). Spectroscopic data show that these complexes contain bent hydrazido ligands, as does 2. Kinetics are consistent with substitution of CO by PR 3 via a dissociative process.

ChemInform Abstract: Coordination Chemistry of Higher Oxidation States. Part 35. Synthetic, Spectroscopic, and Electrochemical Studies of Some mer‐ and fac‐(OsL3X3)/(OsL3X3)+ Systems (L: PR3, AsR3, SbR3, or Pyridine; X: Cl or Br): Crystal Structure of fac‐(Os(PEt2Ph)3Cl3)·CH2Cl2.

AbstractMer‐complexes such as (I) (11 examples) are easily oxidized to (II).

Co-ordination chemistry of higher oxidation states. Part 35. Synthetic, spectroscopic, and electrochemical studies of some mer- and fac-[OsL3X3]/[OsL3X3]+systems (L = PR3, AsR3, SbR3, or pyridine; X = Cl or Br): crystal structure of fac-[Os(PEt2Ph)3Cl3]·CH2Cl2

The complexes mer-[OsL3X3](L = PMe3,PEt3, PEt2Ph, PEtPh2, or AsEt3; X = Cl or Br) are oxidised by HNO3–HBF4 to mer-[OsL3X3]BF4; fac- and mer-[Os(py)3X3]BF4(py = pyridine) were obtained similarly, but attempts to oxidise fac-[OsL′3Cl3](L′= PR3 or AsR3) or mer-[Os(SbPh3)3X3] to OsIV failed. The osmium(IV) complexes were characterised by i.r., u.v.-visible, 31P n.m.r. spectroscopies, magnetic and conductance measurements, and their properties compared with those of the osmium(III) analogues. Cyclic voltammetry showed that most mer-[OsL3X3]0/+ and the fac-[Os(py)3X3]0/+ couples are electrochemically reversible, but fac-[OsL′3Cl3] exhibited only completely irreversible oxidation waves at highly positive potentials. The X-ray structure of fac-[Os(PEt2Ph)3Cl3]·CH2Cl2 has been determined: space group P with a= 18.606(2), b= 10.088(2), c= 10.011 (4)Å;, α= 107.91 (3), β= 97.23(3), γ= 94.85(1)°, and Z= 2; Os–Cl 2.442(3)–2.449(2), Os–P 2.375(2)–2.380(3)Å.

ChemInform Abstract: Manganese(I) Complexes with (Tricyclohexylphosphonio)dithiocarboxylate as Chelate and Unidentate Ligand. X‐Ray Crystal Structure of fac‐(Mn(CO)3(S2CP(C6H11)3)2)ClO4·H2O.

AbstractThe preparation of Mn complexes containing differently bonded types of the title ligand (II) is described.

Synthesis of octahedral carbonyl complexes of manganese(I) with SCN or CN ligands. Crystal structure of fac-[SCNMn(CO) 3(dppm)

The complexes fac-[XMn(CO) 3(dppm)], cis, cis-[XMn(CO) 2(dppm)(P(OPh) 3)] and trans-[XMn(CO)(dppm) 2] with X = SCN or CN have been prepared from the corresponding bromocarbonyls and the salts AgX or KX, or, in the case of the di- and mono-carbonyls, from fac-[XMn(CO) 3(dppm)] with X = SCN or CN by thermal or photochemical CO substitution by the ligands P(OPh) 3 or dppm. The structure of fac-[SCNMn(CO) 3(dppm)] has been determined by X-ray diffraction. The crystals are monoclinic, space group P2 1/ n, and the structure has been refined to R = 0.058 for 4123 reflexions measured in the range 2 ⩽ θ ⩽ 30 at room temperature. The cis, cis-[NCMn(CO) 2(dppm)(P(OPh) 3)] complex can be oxidized and subsequently reduced to the isomer trans-[NCMn(CO) 2(dppm)(P(OPh) 3)]. All the neutral cyanide complexes react readily with MeI and KPF 6 to give the corresponding methylisocyanide derivatives [Mn(CO) 2(dppm)(P(OPh) 3)(CNMe)]PF 6 and [Mn(CO)(dppm) 2(CNMe)]PF 6. The stereochemistries of the compounds is discussed in relation to the 31P NMR spectra.

Crystal structures of fac-[bis(2-diphenylphosphinoethyl)phenylphosphine-PP′P″]tricarbonyl-chromium(0) and -molybdenum(0)

The crystal structures of the title compounds, [M{Ph2P(CH2)2PPh(CH2)2PPh2}(CO)3][(1), M = Cr and (2), M = Mo], have been determined by single-crystal X-ray diffraction methods and refined to residuals of 0.055 and 0.071 for 3 653 and 4 345′ observed' reflections respectively. Crystals of (1) are monoclinic, space group P21, with a= 20.989(9), b= 17.825(10), c= 8.784(4)A, β= 99.70(2)°, and Z= 4; those of (2) are monoclinic, space group P21/n, with a= 15.181(7), b= 18.799(4), c= 12.053(4), β= 106.62(3)°, and Z= 4. In both (1) and (2), the metal–central phosphorus distance is shorter [(1): 2.334(3), 2.328(4); (2): 2.479(2)A] than the metal–terminal phosphorus distances [(1): 2.355(4)—2.391(3); (2): 2.504(3), 2.532(3)A]. In (1) the mean Cr–C length is 1.84 A; in (2), the mean Mo–C length is 1.97 A.

Crystal structure of facial-[bis-(adeninato)(diethylenetriamine)-copper(II)] monohydrate.

The crystal structure of fac-[bis-(adeninato)(dien) copper (II)] monohydrate has been determined from three-dimensional X-ray diffractometer data by heavy atom Fourier methods. Crystals of fac-[Cu (Ade)2 (dien)]·H2O are monoclinic with unit cell dimensions a=16.015 (2), b=14.577 (2), c=7.959 (1) A, β=90.11 (1)°, space group P21/n, and Z=4. Block-diagonal least-squares refinement using 2695 independent reflexions yielded the R value of 0.068. The copper ion assumes a distorted square pyramidal coordination with five coordination sites of which four square planar sites are occupied by the nitrogen N (9) atoms of two unidentate adenine monoanions and the two (terminal and central) nitrogen atoms of tridentate dien, and the axial site (apical position) is occupied by another terminal nitrogen atom of dien. Therefore, the present dien-copper (II) complex takes a bent form (facial coordination). The propensity of adenine to occupy the cis position in equatorial plane of the copper (II) coordination is much stronger than that of dien to take a planar coordination form.