Synthesis and characterization of new metal-metal bonded species. 2. Crystal and molecular structure of dimeric niobium(III) and tantalum(III)bromide adducts with tetrahydrothiophene. Direct stereochemical evidence of bonding electron density in confacial bioctahedra with metal-metal double bonds

Templeton, Joseph L.; Dorman, William Clifford; Clardy, Jon; McCarley, Robert E.

doi:10.1021/ic50183a033

Cited by 37 publications

(11 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Each set has a different Ce-0 bond length average, 2.141 (4), 2.230 (4), and 2.374 (4) Á, respectively. An increase in bond length with increased bridging is common for metal alkoxides.14,15,40…”

Section: Resultsmentioning

confidence: 82%

“…Subsequent addition of NaOCMe3 to this system replaces N03 groups by OCMe3 and forms additional NaN03. This gives, sequentially, the monoalkoxide Ce(OCMe3)(N03)3(THF)2 (1), the dialkoxide Ce(0CMe3)2(N03)2(THF)2 (2), the trialkoxide Ce(0CMe3)3(N03)(THF)2 (3), and the tetraalkoxide Ce-(OCMe3)4(THF)2 (4). When all four NOf groups of CAN are replaced, additional OCMe3" groups attach to cerium to make the anionic complexes Ce(OCMe3)6Na2(THF)4 (5) and Ce2-(OCMe3)9Na (6).…”

Section: Resultsmentioning

confidence: 99%

“…Ce(l)-O(5) 70.1 (2) 0(2)-Ce(l)-0(6) 77.5 (2) 0(2)-Ce(l)-0(8) 75.8 (2) 0(2)-Ce(l)-O(9) 124.1 (2) 0(3)-Ce(l)-G(4) 101.4 (3) 0(3)-Ce(l)-O(5) 129.1(2) 0(3)-Ce(l)-0(6) 79.3 (2) 0(3)-Ce(l)-0(8) 80.7 (2) 0(3)-Ce(l)-0(9) 85.6 (2) 0(4)-Ce(l)-0(5) 80.4 (2) 0(4)-Ce(l)-0(6) 85.4 (2) 0(4)-Ce(l)-C(8) 128.6(2) …”

mentioning

confidence: 99%

See 2 more Smart Citations

Synthetic and structural studies of a series of soluble cerium(IV) alkoxide and alkoxide nitrate complexes

Evans¹,

Deming²,

Olofson³

1989

Inorg. Chem.

115

117

View full text Add to dashboard Cite

The reactions of (NH4)2Ce(N03)6 (CAN) with 2-8 equiv of NaOCMe, in THF and in tert-butyl alcohol have been studied. A series of ceric alkoxide complexes of general formula Ce(OCMe,),(NO,)b(solvent),"d ( a = 1-6; b = 0-3; c = 2, 4; d = 0, 2; a + b = 4 + 6) have been identified as well as Ce2(0CMe3)9Na and Ce3(OCMe3)lo0. Interconversion of these complexes by treatment with NaOCMe, or NH4N03 has also been studied. CAN reacts with 3 equiv of NaOCMe, in THF to form Ce-(OCMe,)(NO3),(THF), (1). In tert-butyl alcohol this reaction forms the HOCMe, solvate Ce(OCMe,)(NO,),(HOCMe,), (1').1 reacts with 1 equiv of NaOCMe, and CAN reacts with 4 equiv of NaOCMe, to form Ce(OCMe3)2(N03)2(THF), (2). In tert-butyl alcohol solvent, 1' reacts with NaOCMe, to form Ce(OCMe3)2(N03)2(HOCMe ), (2'). 2' crystallizes from a concentrated toluene solution at -34 OC in space group Pi (No. 2; Ci) with a = 10.7548 (56) i, b = 11.0853 (49) A, c = 12.4403 (56) A, a = 72.760 (34)O, = 88.190 (39)O, y = 69.050 (35)O, V = 1318.0 (11) A', and Z = 2 for Ddd = 1.41 g cm-,.Least-squares refinement of the model based on 4935 observed reflections converged to RF = 7.7%. If each NO, ligand is taken to occupy just one coordination site, the structure of 2' is that of a distorted octahedron in which identical ligands are trans to each other. Ce(OCMe3),(NOo)(THF)2 (3) can be prepared from 2 or 2' and NaOCMe, or from CAN and 5 equiv of NaOCMe,. Ce(OCMe,),(THF), (4) is prepared from 3 and NaOCMe, or from CAN and 6 equiv of NaOCMe,. The reaction of 4 with 2 equiv of NaOCMe, or reaction of CAN with 8 equiv of NaOCMe, forms Ce(OCMe3)6Na2(THF)4 (5). 5 cr s t a k e s from dimethoxyethane (DME) at -34 OC as Ce (OCMe3)6Na,(DME)2 (5') in space group PnaZl with a = 20.5337 (36) i, b = 10.9557 (23) A, c = 19.4128 (38) A, V = 4367.1 (15) A', and Z = 4 for Dmld = 1.22 gLeast-squares refinement of the model based on 9092 observed reflections converged to RF = 4.9%. 5' contains a distorted-octahedral arrangement of OCMe, groups around cerium. Each sodium ion is coordinated by one DME ligand and a facial set of three OCMe, groups of the Ce(OCMe,)62-octahedron. The reaction of 4 with equiv of NaOCMe, forms Cez(OCMe3)gNa (6). Both 4 and 6 in toluene slowly form Ce,(OCMe3)lo0 (7). Complex 5 reacts with 5 equiv of NH4N03 to form 1 in quantitative yield.

show abstract

Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Synthetic and structural studies of a series of soluble cerium(IV) alkoxide and alkoxide nitrate complexes

Evans¹,

Deming²,

Olofson³

1989

Inorg. Chem.

115

117

View full text Add to dashboard Cite

show abstract

“…As a monomer, the d 2 niobium center could exhibit either singlet or triplet character (Figure a,b, respectively). Dimeric structures are also well-known for several Nb(III) halide complexes ligated with N, , P, ,, and S , donors. Thus, we have also optimized edge-sharing bioctahedral structures in singlet, triplet, and quintet spin states (Figure c–e) based on the known crystal structures with bound acetonitrile.…”

Section: Resultsmentioning

confidence: 98%

Molecular Niobium Precursors in Various Oxidation States: An XAS Case Study

et al. 2018

View full text Add to dashboard Cite

Although X-ray absorption spectroscopy (XAS) has become an indispensable tool in characterization of solidstate materials, it is less of a staple in molecular chemistry of niobium. Scattering X-ray techniques remain relatively unexplored for the systematic study of molecular niobium compounds. Here, we use XAS to probe the niobium environment in commonly used Nb precursors in +V, +IV, and +III oxidation states. Apart from laying out the guidelines for identification of niobium oxidation states, we correlate our data with density functional theory models to provide further structural insight. Of particular note, we are able to shed light on the nature of the commonly used and catalytically competent NbCl 3 (DME), which had not been previously characterized structurally despite its prevalence in Nb chemistry.

show abstract

“…For example, Stiefel and co-workers (1 1) suggested that partial bond formation between adjacent sulfurs could arise through a redox process. In another case McCarley and co-workers ascribed a close contact between two bridging Br atoms to the electrostatic repulsion caused by the electrons in a metal-metal bond (12). The phenomenon has also been discussed by Fackler (13), and by Dance, Wedd, and Boyd (14).…”

Section: Fig 2 Ortep View Of the Anion [C13w(p-s)(p-set)wc112-mentioning

confidence: 85%

Confacial bioctahedral complexes of tungsten(IV) containing tungsten-to-tungsten bonds: X-ray crystal structures of di-μ-ethanethiolato-μ-sulfidobis[dichloro(dimethyl sulfide)-tungsten(IV) (W—W)] and tetraphenylphosphonium di-μ-ethane thiolato-μ-sulfido- bis[trichlorotungstate(IV) (W—W)]

Boorman¹,

Codding²,

Kerr³

et al. 1982

Can. J. Chem.

View full text Add to dashboard Cite

. Can. J. Chem. 60, 1333 (1982).The complex (Me,S)Cl,W(p-S)(p-SEt)zWC1z(Me,S), 1, has been prepared by reaction of [WCI,(Me,S),] with 1 mol-equiv. of SiMe,(SEt) in CH,Cl, solution. A single-crystal X-ray diffraction study shows that the molecule has a confacial bioctahedral structure with a W-W bond length of2.526(2) A. The structure was solved by heavy atom methods and refined to R = 0.061 and R,

show abstract

Synthesis and characterization of new metal-metal bonded species. 2. Crystal and molecular structure of dimeric niobium(III) and tantalum(III)bromide adducts with tetrahydrothiophene. Direct stereochemical evidence of bonding electron density in confacial bioctahedra with metal-metal double bonds

Cited by 37 publications

References 12 publications

Synthetic and structural studies of a series of soluble cerium(IV) alkoxide and alkoxide nitrate complexes

Synthetic and structural studies of a series of soluble cerium(IV) alkoxide and alkoxide nitrate complexes

Molecular Niobium Precursors in Various Oxidation States: An XAS Case Study

Confacial bioctahedral complexes of tungsten(IV) containing tungsten-to-tungsten bonds: X-ray crystal structures of di-μ-ethanethiolato-μ-sulfidobis[dichloro(dimethyl sulfide)-tungsten(IV) (W—W)] and tetraphenylphosphonium di-μ-ethane thiolato-μ-sulfido- bis[trichlorotungstate(IV) (W—W)]

Contact Info

Product

Resources

About