Isoelectronic molecules with triple bonds to metal atoms (M = Mo, W): crystal and molecular structures of tri-tert-butoxytungsten ethylidyne and nitride

1983 ◽  
Vol 22 (20) ◽  
pp. 2903-2906 ◽  
Author(s):  
Malcolm H. Chisholm ◽  
David M. Hoffman ◽  
John C. Huffman
Keyword(s):  
Molecular Structures ◽  
Triple Bonds ◽  
Crystal And Molecular Structures ◽  
Metal Atoms ◽  
Isoelectronic Molecules

Binuclear metal(II) complexes of 1,3-diphenyltriazene : The crystal and molecular structures of the nickel(II), palladium(II) and copper(II) derivatives

1975 ◽  
Vol 28 (11) ◽  
pp. 2377 ◽  
Author(s):  
M Corbett ◽  
BF Hoskins ◽  
NJ McLeod ◽  
BP O'Day
Keyword(s):  
Least Squares Method ◽  
Fourier Method ◽  
Molecular Structures ◽  
Cell Parameters ◽  
Crystal And Molecular Structures ◽  
Metal Atoms ◽  
Metal Metal ◽  
Structure Determinations ◽  
Metal Derivatives ◽  
Binuclear Metal

The crystal and molecular structures have been determined, by single-crystal X-ray methods, for each of the isomorphous set of divalent binuclear metal derivatives of 1,3-diphenyltriazene, abbreviated as dptH, [M(dpt)2]2 where M = Ni, Pd, and Cu. The crystals are composed of discrete molecular units, of composition M2(dpt)4, which have a syn-syn structure analogous to that of copper(II) acetate monohydrate with pairs of closely separated metal atoms held together by the terminal nitrogen atoms of four ligand groups in such a way that the environment of each metal atom is almost square-planar. The interatomic distances between the pairs of metal atoms, 2.395(3), 2563(1), and 2.441(2) Ǻ for the Ni, Pd, and Cu compounds, are strongly suggestive of metal-metal bonding. The two N4-planes are almost parallel but the two sets of coordinating nitrogen atoms are twisted markedly from the eclipsed configuration, the average angle of rotation being about 15°. Crystals of each complex are triclinic with space group P 1. The unit cell parameters in the order of a, b, c, α, β, and γ are 10.335(3), 15.84(1), 13.546(3)& 100.48(5), 94.47(2), 102.57(3)° for Ni2(dpt)4; 10.486(1), 15.791(2), 13.751(1)Ǻ, 99.48(1), 93.61(1), 104.37(1)° for Pd2(dpt)4; 10.373(3), 15.916(5), 13.612(3) Ǻ, 99.51(2), 94.85(3), 102.33(2)° for Cu2(dpt)4. The structure of the nickel complex was solved by the Patterson-Fourier method and the atomic parameters found for this structure were used as the basis of the structure determinations of the isomorphous copper and palladium compounds. All three structures were refined by a block-diagonal least-squares method using 3300 (photographic data) 4065 (counter) and 2753 (counter) independent non-zero terms for the nickel(II), palladium(II) and copper(II) compounds respectively, converging with R values 0.13 (isotropic), 0.056 (anisotropic) and 0.069 (isotropic) respectively.

Crystal and Molecular Structures of Some Alkynyl - Group 9/Group 11 Complexes [M2m4(C2R)8(PPh3)2] (M = Rh, Ir; m = Cu, Ag; R = Ph, Fc (Ir/Cu only))

2003 ◽  
Vol 56 (5) ◽  
pp. 509 ◽  
Author(s):  
Michael I. Bruce ◽  
Natasha N. Zaitseva ◽  
Brian W. Skelton ◽  
Neil Somers ◽  
Allan H. White
Keyword(s):  
Molecular Structures ◽  
Major Contributor ◽  
Crystal And Molecular Structures ◽  
Metal Atoms ◽  
Bonding Mode

The crystal and molecular structures of five complexes [M2m4(C≡ CR)8(PPh3)2] (M = Rh, Ir; m = Cu, Ag; R = Ph, Fc (Ir/Cu only)) are described. Each consists of an approximately octahedral arrangement of the six metal atoms, with atoms M occupying opposite apical positions and atoms m forming an approximate plane. Four alkynyl groups are σ-bonded to each M. Two of these, one from each M, also interact by an asymmetric π-bonding mode with each atom m. Each M is also coordinated to one PPh3 ligand. The M–m distances range between 2.7698(9) and 3.2050(9) Å, although average values fall within the tight ranges 2.86(8) and 2.90(5) (m = Cu) or 3.06(5), 3.09(9) Å (m = Ag). Formally non-bonding M ··· M distances range between 4.1511(8) and 4.654(1) Å, while the shorter m ··· m separations range between 2.659(1) and 2.918(2) Å, which suggests that only weak intermetallic bonding exists. Both the geometries of these complexes and their intense colours suggest that the M2m4 cluster formulation is a major contributor to the structure, rather than a more simplistic, formally zwitterionic assemblage of two [M(C≡ CR)4(PPh3)]2− centres held together by the four m+ cations.

scholarly journals Crystal and molecular structures of two silver(I) amidinates, including an unexpected co-crystal with a lithium amidinate

2016 ◽  
Vol 72 (12) ◽  
pp. 1786-1790 ◽  
Author(s):  
Sida Wang ◽  
Nicole Harmgarth ◽  
Phil Liebing ◽  
Frank T. Edelmann
Keyword(s):  
Triple Bond ◽  
Crystalline State ◽  
Molecular Structures ◽  
Tetrahedral Coordination ◽  
Crystal And Molecular Structures ◽  
Dimeric Structure ◽  
Metal Atoms ◽  
Centrosymmetric Dimers ◽  
Distorted Tetrahedral Coordination ◽  
Linear Coordination

The silver(I) amidinates bis[μ-N1,N2-bis(propan-2-yl)benzamidinato-κ2N1:N2]disilver(I), [Ag2(C13H19N2)2] or [Ag{PhC(NiPr)2}]2(1), and bis(μ-N1,N2-dicyclohexyl-3-cyclopropylpropynamidinato-κ2N1:N2)disilver(I), [Ag2(C18H27N2)2] or [Ag{cyclo-C3H5–C[triple-bond]C–C(NCy)2}]2(2a), exist as centrosymmetric dimers with a planar Ag2N4C2ring and a common linear coordination of the metal atoms in the crystalline state. Moiety2aforms a co-crystal with the related lithium amidinate, namely bis(μ-N1,N2-dicyclohexyl-3-cyclopropylpropynamidinato-κ2N1:N2)disilver(I) bis(μ-N1,N2-dicyclohexyl-3-cyclopropylpropynamidinato-κ3N1,N2:N1)bis(tetrahydrofuran-κO)lithium(I) toluene monosolvate, [Ag2(C18H27N2)2][Li2(C18H27N2)2(C4H8O)2]·C7H8or [Ag{cyclo-C3H5–C[triple-bond]C–C(NCy)2}]2[Li{cyclo-C3H5–C[triple-bond]C–C(NCy)2}(THF)]2·C7H8, composed as2a×2b× toluene. The lithium moiety2bfeatures a typical ladder-type dimeric structure with a distorted tetrahedral coordination of the metal atoms. In the silver(I) derivatives1and2a, the amidinate ligand adopts a μ-κN:κN′ coordination, while it is a μ-κN:κN:κN′-coordination in the case of lithium derivative2b.

A Solvent-Dependent and Electrochemically Controlled Self-Assembling/Disassembling System

2003 ◽  
Vol 68 (9) ◽  
pp. 1647-1662 ◽  
Author(s):  
Valeria Amendola ◽  
Massimo Boiocchi ◽  
Yuri Diaz Fernandez ◽  
Carlo Mangano ◽  
Piersandro Pallavicini
Keyword(s):  
Equilibrium Mixture ◽  
Bidentate Ligand ◽  
Molecular Structures ◽  
The Self ◽  
Molar Ratio ◽  
Crystal And Molecular Structures ◽  
Self Assembling ◽  
Irreversible Oxidation ◽  
Irreversible Reduction ◽  
Metal Ligand

The bis-bidentate ligand R,S-1,2-diphenyl-N,N'-bis(2-quinolinemethylidene)ethane-1,2-diamine (ligand 4), containing two (iminomethyl)quinoline moieties separated by a cis-1,2-diphenylethylene spacer, forms stable complexes with both CuI and CuII. With CuII, the monomeric 1:1 complex [CuII(4)]2+ is obtained both in CH3CN and CH2Cl2. With CuI and overall 1:1 metal/ligand molar ratio, an equilibrium mixture is obtained in CH3CN, consisting of [CuI(4)2]+, [CuI2(4)2]2+ and [CuI2(4)(CH3CN)4]2+. The preponderant species is the two-metal one-ligand "open" complex [CuI2(4)(CH3CN)4]2+, in which each Cu+ cation is coordinated in a tetrahedral fashion by one (iminomethyl)quinoline unit and by two CH3CN molecules. Precipitation from the equilibrium mixture yields only crystals of [CuI2(4)(CH3CN)4](ClO4)2·2CH3CN, whose crystal and molecular structures have been determined. On the other hand, in the poorly coordinating CH2Cl2 solvent, only the dimeric helical [CuI2(4)2]2+ complex is obtained, when the overall metal/ligand 1:1 molar ratio is chosen. Addition of large quantities of acetonitrile to solutions of [CuI2(4)2]2+ in dichlorometane results in the formation of [CuI2(4)(CH3CN)4]2+, i.e. in the solvent-driven disassembling of the CuI helicate. While electrochemistry in CH3CN is poorly defined due to the presence of more than one CuI species, cyclic voltammetry experiments carried out in CH2Cl2 revealed a well defined behavior, with irreversible oxidation of [CuI2(4)2]2+ and irreversible reduction of [CuII(4)]2+ taking place at separate potentials (∆E ≈ 700 mV). Irreversibility and separation of the redox events are due to the self-assembling and disassembling processes following the reduction and oxidation, respectively.

Synthesis of Trispirocyclotriphosphazenes with Oxaphosphorine Rings and Their Crystal and Molecular Structures

2021 ◽  
Vol 60 (7) ◽  
pp. 5014-5020
Author(s):  
Yuji Tada ◽  
Atsushi Sunada ◽  
Riki Watanabe ◽  
Makoto Kanazawa ◽  
Keiichiro Utsumi
Keyword(s):  
Molecular Structures ◽  
Crystal And Molecular Structures

Novel Synthetic Routes to s-Block Metal 2,5-Diphenylphospholides and Crystal Structures of the Bis(tetrahydrofuran) Complexes of the Potassium, Calcium, and Strontium Derivatives

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1360-1368 ◽  
Author(s):  
Katja Wimmer ◽  
Christin Birg ◽  
Robert Kretschmer ◽  
Tareq M.A. Al-Shboul ◽  
Helmar Görls ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Chain Structure ◽  
Molecular Structures ◽  
Metathesis Reaction ◽  
Sandwich Complex ◽  
Coordination Site ◽  
Metal Atoms ◽  
Synthetic Routes ◽  
A Chain

The reduction of 1,4-diphenyl-1,4-bis(diphenylphosphanyl)buta-1,3-diene (1) (1,4-diphenyl- NUPHOS) with potassium in THF yields bis(THF)potassium 2,5-diphenylphospholide (2) which crystallizes with a chain structure. The metathesis reaction of 2 with the iodides of calcium, strontium, and barium leads to the formation of [bis(THF)calcium bis(2,5-diphenylphospholide)] (3), [bis(THF)strontium bis(2,5-diphenylphospholide)] (4), and [bis(THF)barium bis(2,5-diphenylphospholide)] (5). The reaction of M{P(H)SiiPr3}2 with diphenylbutadiyne in THF also leads to the formation of the 2,5-diphenylphospholides of calcium (3), strontium (4), and barium (5). The molecular structures of 2 to 4 are discussed. The environment of the metal atoms is very similar in all these compounds: The metal atoms show an η5 coordination to the phospholide rings forming a bent sandwich complex. The open coordination site is occupied by two THF molecules

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