Unique Capping Position Research Articles

Synthesis, structure and properties of the mixed-ligand tungsten(II) complex [WBr2(CO)3(tmpymt)] (tmpymt = 1,4,6-trimethylpyrimidine-2-thione)

In the mononuclear seven-coordinated complex [WBr 2 (CO) 3 (tmpymt)]·C 3 H 6 O the W II atom adopts a distorted capped trigonal prism (CTP) geometry. The single-crystal X-ray molecular structure was compared to the optimized molecular structure (RHF/LanL2DZ) and the results are convergent to CTP geometry. The reaction of [{WBr(CO) 4 } 2 (μ-Br) 2 ] 2 1 with 1,4,6-trimethylpyrimidine-2-thione (tmpymt) affords the air-sensitive complex [WBr 2 (CO) 3 (tmpymt)] 2 . The X-ray structure of 2 ·C 3 H 6 O reveals that the geometry surrounding the tungsten(II) atom is best described as a distorted capped trigonal prism with a bromine atom Br(1) in the unique capping position. The other bromine atom Br(2), the (N,S)-chelate and one carbonyl C(41) occupy the capped quadrilateral face. The complex has been additionally characterized by IR and NMR spectroscopy. The optimized molecular structure (RHF/LanL2DZ) supports the experimental data.

Crystal structures of [WI2(CO)3{Ph2P(CH2)nPPh2}] (n = 2 or 3)

[WI2(CO)3{Ph2P(CH2)2PPh2}] (1) crystallizes out in the monoclinic space group P21/n, with a = 13.852(7) A, b = 14.789(19) A, c = 14.915(19) A, β = 102.86(1)°, Z = 4. [WI2(CO)3{Ph2P(CH2)3PPh2}] (2) crystallizes out in the monoclinic space group P21/n, with a = 10.499(15) A, b = 14.58(2) A, c = 20.75(3) A, β = 103.59(1)°, Z = 4. Both structures show the metal in a seven-coordinate environment with a carbonyl in the unique capping position, two further carbonyls and a phosphorus in the capped face, and two iodides and the second phosphorus in the uncapped face.

A novel Mo–Sn chlorocarbonyl compound. X-ray crystal structure of [(CO) 4Mo(μ-Cl) 3Mo(SnCl 3)(CO) 3] and [MoCl(SnCl 3)(CO) 3(NCEt) 2

The new heterobimetallic complex [(CO) 4Mo(μ-Cl) 3Mo(SnCl 3)(CO) 3] ( 1) has been prepared by photochemical reaction of Mo(CO) 6 with SnCl 4. The structure of complex 1 was established by X-ray crystallography. The basic structural units of 1 are two seven-coordinate molybdenum atoms, which are linked by three chlorine atoms occupying a bridging position between the molybdenum atoms. The mononuclear seven-coordinate complex [MoCl(SnCl 3)(CO) 3(NCMe) 2] ( 2) is formed by reaction of [(CO) 4Mo(μ-Cl) 3Mo(SnCl 3)(CO) 3] with acetonitrile. Treatment of compound 2 with propionitrile affords [MoCl(SnCl 3)(CO) 3(NCEt) 2] ( 3). A single-crystal X-ray diffraction study of the complex [MoCl(SnCl 3)(CO) 3(NCEt) 2] ( 3) showed that the environment of the molybdenum atom is a distorted capped octahedron with the SnCl 3 anionic ligand occupying the unique capping position above an octahedral face defined by the bridging chlorine and two carbonyl groups.

Monodentately coordinated o-phenylenediacetonitrile seven-coordinate complexes of molybdenum(II) and tungsten(II): X-ray crystal structure of [WI 2(CO) 3{1,2-C 6H 4(CH 2CN) 2- N} 2

Treatment of [MI 2(CO) 3(NCMe) 2] (M=Mo or W) with 2 equiv. of o-phenylenediacetonitrile (1,2-C 6H 4(CH 2CN) 2) gives the complexes [MI 2(CO) 3{1,2-C 6H 4(CH 2CN) 2- N} 2] ( 1 and 2) via displacement of the acetonitrile ligands. The tungsten complex [WI 2(CO) 3{1,2-C 6H 4(CH 2CN) 2- N} 2] ( 2) has been characterised crystallographically. The geometry surrounding the coordination sphere is capped octahedral with a carbonyl group in the unique capping position, an iodide and two carbonyls in the capped face and an iodide and two nitrogen atoms from nitrile groups in the uncapped face. Reactions of 1 and 2 with equimolar amounts of L (L=PPh 3, AsPh 3, SbPh 3, P(OPh) 3) affords [MI 2(CO) 3(NCMe)L], which followed by an in situ reaction with 1 equiv. of 1,2-C 6H 4(CH 2CN) 2 gives the new mixed ligand complexes [MI 2(CO) 3{1,2-C 6H 4(CH 2CN) 2- N}L] ( 3– 10) in high yield. Reaction of [MI 2(CO) 3(NCMe) 2] and [MI 2(CO) 3(NCMe)(PPh 3)] with 2 and 1 equiv. of L 1 (L 1=[WI 2(CO) 3{1,2-C 6H 4(CH 2CN) 2- N} 2] ( 2)) gives the first trimetallic [MI 2(CO) 3L 1 2] ( 11 and 12) and bimetallic [MI 2(CO) 3L 1(PPh 3)] ( 13 and 14) o-phenylene diacetonitrile bridged complexes in high yield.

Molecular structure and iodine oxidative-thermal decarbonylation of the seven-coordinate complex [MoI2(CO)3(NCMe)2] to give the crystallographically characterised complex mer-[MoI3(NCMe)3

The X-ray crystal structure of the seven-coordinate complex [MoI2(CO)3(NCMe)2] (1) has been determined and shows discrete molecules. The geometry of the metal coordination sphere conforms to a distorted capped octahedron with a carbonyl group in the unique capping position. The capped face contains two carbonyl ligands and an iodo group, the uncapped face two MeCN ligands and an iodo group. The low temperature 13C n.m.r. spectrum (−70 °C, CD2Cl2) shows a single band at δ = 222.8 ppm, which suggests that the complex is rearranging more rapidly than the n.m.r. timescale at this temperature. Refluxing a 2:1 mixture of [MoI2 (CO)3(NCMe)2] and I2 in MeCN for 2h gives the crystallographically characterised molybdenum(III) complex mer-[MoI3(NCMe)3] (2) in quantitative yield.

Synthesis, structure and reactivity of novel W–Ge chlorocarbonyl compounds. X-ray crystal structure of [WCl(GeCl 3)(CO) 3(NCEt) 2

The reaction of GeCl 4 with tungsten(0) compounds yielded heterobimetallic W–Ge complexes. The novel dinuclear complex [(CO) 4W( μ-Cl) 3W(GeCl 3)(CO) 3] 1 was obtained together with [W(CO) 5(GeCl 2)] 2 in a photochemical reaction of W(CO) 6 with GeCl 4. The mononuclear seven-coordinate complex [WCl(GeCl 3)(CO) 3(NCMe) 2] 3 was formed in a reaction of complex 1 with acetonitrile or in a reaction of [W(CO) 4(NCMe) 2] with GeCl 4 in dichloromethane. A single-crystal X-ray diffraction study of the complex [WCl(GeCl 3)(CO) 3(NCEt) 2] 4 showed that the environment of the tungsten atom is a distorted capped octahedron with the GeCl 3 anionic ligand occupying the unique capping position above an octahedral face defined by the three carbonyl groups. The position of the GeCl 3 ligand is approximately trans to the W–Cl bond. The dinuclear complex 1 and the mononuclear complex 3 show similar behavior in reaction with alkynes. Complexes were isolated in which CO or/and acetonitrile ligands were replaced by alkyne ligands. The alkyne tungsten(II) complexes 7–13 formed were structurally characterized by IR and NMR spectroscopy. However, the reaction of 1 and 3 with phenylacetylene (PA) leads to polymerization and formation of a high molecular weight polyphenylacetylene (PPA). The structures and mechanisms of the formation of various new types of complexes and their role in the catalytic process are discussed.

Seven-coordinate thiophene-3-acetonitrile complexes of tungsten(II). Crystal structures of [WI 2(CO) 3{NCCH 2(3-C 4H 3S)} 2] and [WI 2(CO) 3{NCCH 2(3-C 4H 3S)}(AsPh 3)

Reaction of [WI 2(CO) 3(NCMe) 2] with 2 equivalents of thiophene-3-acetonitrile {NCCH 2(3-C 4H 3S)} gave the crystallographically characterised complex [WI 2(CO) 3{NCCH 2(3-C 4H 3S)} 2] ( 1). The structure of 1 can be described as a distorted capped octahedron with a carbonyl group in the capping position, two carbonyl groups and an iodide in the capped face and two acetonitrile ligands and an iodide in the uncapped face. Treatment of the seven-coordinate complex [WI 2(CO) 3(NCMe) 2] with an equimolar amount of L {L=AsPh 3 ( 2) or PPh 3 ( 3)} followed an in situ reaction with by one equivalent of thiophene-3-acetonitrile afforded the mixed ligand complexes [WI 2(CO) 3{NCCH 2(3-C 4H 3S)}L] { 2 (crystallographically characterised) and 3}. The structure of 2 also has a capped octahedral geometry, again having a carbonyl ligand in the unique capping position.

Seven-coordinate complexes of molybdenum(II) and tungsten(II) containing pyridine-2-thionate and pyrimidine-2-thionate. Crystal structure of [W(CO) 3( η2-pymS) 2] (pymS = pyrimidine-2-thionate)

Reaction of [WI 2(CO) 3(NCMe) 2] with two equivalents of K[pymS] (pymS = pyrimidine-2-thionate) has given the crystallographically characterised complex [W(CO) 3( η 2-pymS) 2] ( 1).The structure can be described as a distorted monocapped trigonal prism with a carbonyl ligand in the unique capping position. Equimolar quantities of [MI 2(CO) 3(NCMe) 2] and L{for M = Mo or W, L = PPh 3; for M = W only, L = PPh 2Cy or PPh 2Nap (Nap = napthyl)} react to give [MI 2(CO) 3(NCMe)L], followed by reaction in situ with K[pyS or pymS] (pyS = pyrimidine-2-thionate) afforded the complexes [MI(CO) 3L( η 2-pyS or pymS)] ( 2–7). The tungsten complexes [WI 2(CO) 3LL′] {L = L′ = PPh 3, PPh 2Cy, PPh 2Nap or L = PPhBz 2, L′ = AsPh 3; L = PPh 3, L′ = PPh 2Bz, PPhBz 2, AsPh 3 or SbPh 3} (prepared in situ) react with an equimolar amount of K[pymS] to give the S-monodentately coordinated pyrimidine-2-thionate complexes [WI(CO) 3LL′( η 1-S-pymS)] ( 8–15). Similarly, treatment of [WI 2(CO) 3{Ph 2P(CH 2) n PPh 2}] ( n = 1–6 ) (prepared in situ) with one equivalent of K[pyS] or K[pymS] yielded the monodentately attached pyrimidine-2-thionate or pyridine-2-thionate complexes [WI(CO) 3{Ph 2P(CH 2) n PPh 2}( η 1-S-pyS or -S-pymS)]( 16–27). The molybdenum complex [MoI 2(CO) 3{Ph 2P(CH 2) 2PPh 2}] (prepared in situ) reacts with an equimolar amount of K[pymS] to give the bidentately coordinated pyrimidine-2-thionate dicarbonyl complex MoI(CO) 2{Ph 2P(CH 2) 2PPh 2}( η 2-pymS)] ( 28).

Six- and seven-co-ordinate complexes of molybdenum(II) and tungsten(II) with thioether ligands. Crystal structures of [WI2(CO)3{4-MeC6H4S(CH2)2SC6H4Me-4}] and [WI2(CO)2{MeS(CH2)2S(CH2)2SMe-S,S′,S″}

Reaction of [MI2(CO)3(NCMe)2](M = Mo or W) with a slight excess of RS(CH2)2SR (R = Ph, 4-MeC6H4 or 4-FC6H4) in CH2Cl2 at room temperature gave [MI2(CO)3{RS(CH2)2SR}]. The molecular structure of [WI2(CO)3{4-MeC6H4S(CH2)2SC6H4Me-4}] has been determined by X-ray crystallography. It shows that the tungsten has essentially capped-octahedral geometry with a carbonyl ligand in the unique capping position. Low-temperature 13C NMR studies on the tungsten complexes suggest that their structures in solution are similar to the solid-state structure found. Reaction of [WI2(CO)3(NCMe)2] with 2 equivalents of PhS(CH2)2SPh in CH2Cl2 afforded [WI(CO)3{PhS(CH2)2SPh-S}{PhS(CH2)2SPh-S,S′}]I which was reduced by LiBun to cis-[W(CO)2{PhS(CH2)2SPh-S.S′}2]. Equimolar quantities of [MI2(CO)3(NCMe)2](M = Mo or W) and MeS(CH2)2S(CH2)2SMe reacted in CH2Cl2 to give [MoI2(CO)2{MeS(CH2)2S(CH2)2SMe-S,S″,S″}] and [WI2(CO)3{MeS(CH2)2S(CH2)2SMe-S,S″}]. The latter was converted in CHCl3 into [WI2(CO)2{MeS(CH2)2S(CH2)2SMe-S,S″,S″}], the molecular structure of which is essentially a capped octahedron with a carbonyl ligand in the unique capping position.

ChemInform Abstract: Synthesis and Spectroscopic Properties of Some New Seven‐Coordinate Thioacetamide Complexes of Molybdenum(II) and Tungsten(II).

AbstractEquimolar quantities of (I) and (II) react to give initially (IV) or the corresponding Mo derivative in the case of (Ia), which rapidly dimerizes to yield (III).

Synthesis and spectroscopic properties of some new seven-coordinate thioacetamide complexes of molybdenum(II) and tungsten(II)

The compounds [MI 2(CO) 3(NCMe) 2] (M = Mo or W) react with one equivalent of SC(NH 2)Me in CH 2Cl 2 at room temperature to initially give the acetonitrile substituted products [MI 2(CO) 3(NCMe)- {SC(NH 2)Me}] which was isolated for M = W. However, the molybdenum complex rapidly dimerizes with loss of acetonitrile to give the iodide-bridged compound [Mo(σ-I)I(CO) 3 {SC(NH 2)Me}] 2. The tungsten complex does not appear to dimerize, even after stirring at room temperature for 72 h in CH 2Cl 2. Two equivalents of thioacetamide react with [MI 2- (CO) 3(NCMe) 2] in CH 2Cl 2 at room temperature to give the new bisthioacetamide compounds [MI 2- (CO) 3{SC(NH 2)Me} 2] via displacement of the labile acetonitrile ligands. The low temperature (−70 °C) 13C NMR spectrum of [WI 2(CO) 3{SC(NH 2)Me} 2] indicates that the geometry of the complex is capped octahedral with a carbonyl ligand in the unique capping position.

X-ray crystal structure and 13C NMR spectra of [WI2(CO)3(NCMe)2

Abstract The X-ray crystal structure of [WI 2 (CO) 3 (NCMe) 2 ] ( 1 ) was determined and the crystals are orthorhombic with a = 12.405(8), b = 7.590(8), c = 13.844(12) A. X-ray data for 911 independent reflections above background were collected on a diffractometer and the structure determined by Fourier methods and refined to R = 0.074. The tungsten geometry is capped octahedral with a carbonyl ligand in the unique capping position. The iodide ligands are trans to each other with the two acetonitrile and octahedral carbonyl ligands cis to each other. The low temperature (−70°C, CD 2 Cl 2 ) 13 C NMR spectrum of ( 1 ) showed carbonyl resonances at δ = 202.36 and 228.48 ppm with an intensity ratio of 2 : 1. The resonance at lower field can be ascribed to the carbonyl ligand in the unique capping position. However, the room temperature 13 C NMR spectrum of ( 1 ) shows a single carbonyl resonance at δ = 219.65 ppm.

Synthesis and spectroscopic properties of the ‘mixed’ seven-co-ordinate complexes [MI2(CO)3L(L′)][M = Mo or W; L,L′= PPh3, PPh2(C6H11), PPh(C6H11)2, AsPh3, or SbPh3] and rearrangement of selected [MI2(CO)3L(L′)] to [HL][MI3(CO)3L′]. X-Ray crystal structure of [PPh2(C6H11)H][WI3(CO)3(SbPh3)]·Et2O

Reaction of the complexes [MI2(CO)3(NCMe)2](M = Mo or W) with 1 equivalent of L(L = PPh3, AsPh3, or SbPh3) in CH2Cl2 at room temperature followed by 1 equivalent of L′[L′= PPh3, PPh2(C6H11), PPh(C6H11)2, AsPh3, or SbPh3]in situ affords the ‘mixed’ seven-co-ordinate compounds [MI2(CO)3L(L′)]. Low-temperature (-70 °C, CD2Cl2)13C n.m.r. spectra of the triphenylantimony complexes [MI2(CO)3L(SbPh3)][L = PPh3, PPh2(C6H11), or PPh(C6H11)2] showed two carbonyl resonances. This indicated capped octahedral geometry with a carbonyl ligand in the unique capping position. Some of the neutral seven-co-ordinate complexes [MI2(CO)3L(L′)] containing phosphines disproportionated in CH2Cl2 to give the salts [HL][MI3(CO)3L′]. 31P N.m.r. spectroscopy and negative ion mass spectrometry confirmed that the more electron-rich phosphine is protonated in [HL][MI3(CO)3(PPh3)][L = PPh2(C6H11) or PPh(C6H11)2]. The structure of the complex [PPh2(C6H11)H][WI3(CO)3(SbPh3)]·Et2O was determined by X-ray analysis. The co-ordination geometry about the tungsten is capped octahedral with a carbonyl ligand in the unique capping position. The capped face contains two carbonyl groups and the triphenylantimony ligand, with the three iodide ligands occupying the uncapping face. The low-temperature (-70 °C, CD2Cl2) spectrum of the related complex [NBun4][WI3(CO)3(SbPh3)] prepared by treating [WI2(CO)3(NCMe)(SbPh3)]in situ with 1 equivalent of [NBun4]I in CH2Cl2showed two carbonyl resonances at δ= 209.68 and 235.50 p.p.m. with an intensity ratio of 2 : 1. The lower-field resonance can be ascribed to the unique capping carbonyl ligand and the higher-field resonance to the two equivalent carbonyl ligands on the octahedron. The low-temperature 13C n.m.r. spectrum of [NBun4][MoI3(CO)3(PPh3)] shows a single resonance at δ= 222.20 p.p.m. which suggests a different capped octahedral structure with the triphenylphosphine ligand capping the three carbonyl ligands.

New synthesis of seven-coordinate complexes of molybdenum(II) and tungsten(II) containing bidentate phosphorus ligands, [MI 2(CO) 3{Ph 2P(CH 2) nPPh 2}] ( n = 1–6)

A new high yielding synthesis of the seven-coordinate complexes [MI 2(CO) 3{Ph 2P(CH 2) n PPh 2}] (M = Mo and W; n = 1–6) is described. The procedure involves reacting the complexes [MI 2(CO) 3(NCMe) 2] in CH 2Cl 2 with an equimolar amount of the bidentate phosphorus ligand. The low temperature (−70 °C) 13C NMR spectra of the complexes [Wl 2(CO) 3{Ph 2P(CH 2) n PPh 2}] ( n = 3 and 5) indicates that the geometry is capped octahedral with a carbonyl ligand in the unique capping position.

Phosphine containing rhenium(III) carbonyl complexes. The crystal and molecular structure of tribromodicarbonylbis(dimethyl-phenylphosphine)rhenium(III)

Bromine oxidation of [ReBr(CO) 3(PR 3) 2] [PR 3 = PMe 2Ph, PEt 2Ph, PMePh 2, PPh 3, PPh 2C 6H 4Me-4 or P(C 6H 4OMe-4) 3] yields stable seven-coordinate rhenium(III) complexes [ReBr 3(CO) 2(PR 3) 2] only for the less sterically demanding phosphines PMe 2Ph, PEt 2Ph and PMePh 2. Crystals of [ReBr 3(CO) 2(PMe 2Ph) 2] ( 1) are triclinic, space group P 1 − , Z = 2, in a unit cell with lattice parameters a = 9.575(8), b = 14.705(11), c = 9.629(12) Å, α = 77.71(7), β = 109.06(8) and γ = 115.02(8)°. 2991 independent reflections above background were collected on a diffractometer and refined to R0.07. The metal atom has a capped octahedral environment with a carbonyl in the unique capping position [1.87(3) Å], two phosphines [2.456(13), 2.496(11) Å] and one carbonyl 1.85(5) Å in the capped face, and three bromine atoms in the uncapped face [2.589(5), 2.623(6), 2.622(5) Å]. Attempts to convert ( 1) to the six-coordinate d 4 cation [ReBr 2(CO) 2(PMe 2Ph) 2] + for structural comparison with the isoelectronic Group 6 analogues [MBr 2(CO) 2(PR 3) 2] (M = Mo or W) were unsuccessful.

Stereochemistry of seven-co-ordinate complexes containing a tin–molybdenum bond: crystal structure of [1,2-bis(diphenylphosphino)- ethane]tetracarbonyl(trichlorostannyl)molybdenum(I) aquapentachloro-stannate–benzene

Crystals of the title compound are monoclinic with a= 21.846(5), b= 12.346(3), c= 20.486(6)A, β= 122.23(2)°, Z= 4, space group =P21/c. The structure was solved from 2 149 observed diffractometer intensities by the symbolic addition method and refined by least-squares methods to R 9.4%. The cation has monocapped octahedral geometry with the SnCl3 group bonded to the central molybdenum atom in the unique capping position [Mo–Sn 2.729(4)A]. Three carbonyl groups define the capped face, while the bidentate ligand and the remaining carbonyl group make up the uncapped face. The anion has the expected irregular octahedral geometry. The stereochemistry of the cation is compared with that of relevant seven-co-ordinate molecules containing Mo–Sn and W–Sn bonds.

Crystal and molecular structure of tetracarbonyliodo-[ o-phenylenebis(dimethylarsino)] tungsten(II) triiodide

Crystals of the title compound are monoclinic, spacegroup P2 1/ m; a = 14.43(1), b = 10.86(1), c = 8.01(1) Å β = 93.51(8)°; Z = 2. The structure was solved from diffractometer data by Patterson and Fourier methods and refined by least squares to R 0.07 for 1544 independent reflections. The cations have crystallographic m symmetry with the metal and iodine atoms on the mirror plane. The metal atom has a capped trigonal prismatic environment with the iodine atom in the unique capping position [2.842(3) Å], two arsenic atoms [2.636(2) Å] and two carbonyl groups [2.067(24) Å] in the capped quadrilateral face and two carbonyl groups [1.988(25) Å] in the remaining edge. The distortions of the geometry from the ideal are very small despite the variations in ligand type in the quadrilateral face. The triiodide anion is asymmetrical with dimensions [2.895(3), 2.957(4) Å, 178.6(1)°].

ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE OF DICARBONYLCHLOROBIS‐(O‐PHENYLENE(DIMETHYLARSINO))MOLYBDENUM(II) TRI‐IODIDE‐BISCHLOROFORM

Crystals of the title compound are orthorhombic, space group Pnma, with a= 11·75(1), b= 15·27(1), c= 24·15(2)A, Z= 4. The structure was solved by the heavy-atom method from 1048 independent reflections, collected by counter methods, and refined by full-matrix least-squares techniques to R 0·080. The symmetry of the cation is very close to C2v(mm) with one of the mirror planes imposed by the space group. Thus the molybdenum atom has a 1,4,2-capped trigonal prismatic environment with a chlorine atom in the unique capping position [2·575(11)A], four arsenic atoms in the capped quadrilateral face [2·614(5), 2·617(5)A], and two carbonyl groups making up the remaining edge [1·92(5), 1·87(5)A]. The tri-iodide ion lies with the central atom on a crystallographic mirror plane [2·903(2)A, 176·9(2)°].

ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE OF 2,2′‐BIPYRIDYLDICHLORO(TRIMETHYL)‐TANTALUM(V)

Chemischer InformationsdienstVolume 4, Issue 46 Organoelement Compounds ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE OF 2,2′-BIPYRIDYLDICHLORO(TRIMETHYL)-TANTALUM(V) MICHAEL G. B. DREW, MICHAEL G. B. DREWSearch for more papers by this authorJOHN D. WILKINS, JOHN D. WILKINSSearch for more papers by this author MICHAEL G. B. DREW, MICHAEL G. B. DREWSearch for more papers by this authorJOHN D. WILKINS, JOHN D. WILKINSSearch for more papers by this author First published: November 13, 1973 https://doi.org/10.1002/chin.197346365AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume4, Issue46November 13, 1973 RelatedInformation

Crystal and molecular structure of dicarbonylchlorobis-[o-phenylene(dimethylarsino)]molybdenum(II) tri-iodide–bischloroform

Crystals of the title compound are orthorhombic, space group Pnma, with a= 11·75(1), b= 15·27(1), c= 24·15(2)A, Z= 4. The structure was solved by the heavy-atom method from 1048 independent reflections, collected by counter methods, and refined by full-matrix least-squares techniques to R 0·080. The symmetry of the cation is very close to C2v(mm) with one of the mirror planes imposed by the space group. Thus the molybdenum atom has a 1,4,2-capped trigonal prismatic environment with a chlorine atom in the unique capping position [2·575(11)A], four arsenic atoms in the capped quadrilateral face [2·614(5), 2·617(5)A], and two carbonyl groups making up the remaining edge [1·92(5), 1·87(5)A]. The tri-iodide ion lies with the central atom on a crystallographic mirror plane [2·903(2)A, 176·9(2)°].