Crystal and molecular structures of three transition metal complexes incorporating the anionic tridentate chelating ligands [Me2Ga(N2C5H7)OCH2CH2SR]− where R = Et or Ph

1981 ◽  
Vol 59 (15) ◽  
pp. 2391-2401 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Molecular Structures ◽  
Distorted Octahedral Geometry ◽  
The Novel ◽  
Space Group ◽  
Bond Lengths ◽  
Tetrahedral Environment ◽  
Distorted Octahedral

X-ray crystallographic studies of three transition metal complexes incorporating the novel anionic tridentate chelating ligand [Me2Ga(N2C5H7)OCH2CH2SR]− (R = Et or Ph) show that the ligand is facially coordinated in each case. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl) (2-thioethoxyethoxy)gallato(N(2), O,S)]nitrosylnickel(I) are monoclinic, a = 8.8313(4), b = 7.2402(2), c = 26.539(1) Å, β = 94.390(3)°, Z = 4, space group P21/c, R = 0.040 and Rw = 0.050 for 2489 reflections. The Ni atom is in a distorted tetrahedral environment with bond angles about Ni ranging from 87.90(7) to 127.9(1)°. The nitrosyl coordination is slightly non-linear with Ni—N—O = 170.1(4)°. Important bond lengths (corrected for libration) are: Ni—S, 2.326(1), Ni—O, 2.019(2), Ni—N(pyrazolyl), 1.980(3), Ni—N(O), 1.633(3) and N—O, 1.156(4) Å. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl) (2-thiophenoxyethoxy)gallato(N(2),O,S)]tricarbonylmanganese(I) are triclinic, a = 9.4911(5), b = 10.4323(6), c = 11.7618(7) Å, α = 86.17(1), β = 69.547(5), γ = 81.402(4)°, Z = 2, space group [Formula: see text]R = 0.029 and Rw = 0.035 for 2496 reflections. The Mn atom is coordinated to the fac-tridentate gallate ligand and to three carbonyl ligands resulting in a slightly distorted octahedral geometry. Important corrected bond lengths are: Mn—S, 2.397(1), Mn—O, 2.055(2), Mn—N, 2.082(3), and Mn—C, 1.794(4), 1.807(4), and 1.807(4) Å. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl) (2-thioethoxyethoxy)gallato(N(2),O,S)](η3-cycloheptatrienyl)dicarbonylmolybdenum are monoclinic, a = 17.030(3), b = 19.097(2), c = 15.908(3) Å, β = 115.99(1)°, Z = 8, space group P21/n R =0.036 and Rw = 0.043 for 4477 reflections. The two crystallographically independent molecules differ primarily in the orientation of the S-ethyl moiety and each contains an η3-C7H7 ligand which occupies one coordination site of a distorted octahedron as a %-donating ligand. Important corrected bond distances are: Mo—S, 2.527(2) and 2.541(2), Mo—O, 2.241(5) and 2.237(4), Mo—N, 2.277(5) and 2.254(5), Mo—C(O), 1.940(7)–1.960(7), and Mo—C(C7H7), 2.198(6)−2.391(7) Å.

Synthesis, characterization, and X-ray structural studies of octahedral transition metal complexes incorporating the novel anionic tridentate ligand, dimethyl(ethanolamino)(1-pyrazolyl)- gallate, [Me2Ga(OCH2CH2NH2)(N2C3H3)]−

1978 ◽  
Vol 56 (9) ◽  
pp. 1212-1221 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Tridentate Ligand ◽  
The Novel ◽  
Structural Studies ◽  
Space Group ◽  
X Ray ◽  
Distorted Octahedral Coordination Geometry ◽  
Distorted Octahedral

Details of the synthesis and physical properties of octahedral transition metal complexes of the tridentate tris chelating ligand [Me2Ga(OCH2CH2NH2)(N2C3H3)]− are given. Crystals of sym-fac-bis[dimethyl(ethanolamino)(1-pyrazolyl)gallato(N(2),O,N]nickel(II) are monoclinic, a = 11.7908(6), b = 7.3158(6), c = 12.5797(8), β = 97.035(7)°, Z = 2, space group P21/n and crystals of the mer isomer are monoclinic, a = 18.6617(7), b = 8.7941(4), c = 13.5670(8), β = 91,766(4)°, Z = 4, space group P21/c. The structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to final R values of 0.048 and 0.052 for 1881 and 2573 reflections with I ≥ 3σ(I) for the fac and mer isomers respectively. The nickel atoms in both structures were found to have distorted octahedral coordination geometry. Bond lengths (corrected for libration) are: Ni—O, 2.090(3); Ni—N, 2.085(3) and 2.112(3); Ga—O, 1.908(3); Ga—N, 2.010(3); and Ga—C, 1.979(5) and 1.981(6) Å for the fac isomer, and Ni—O, 2.045(4) and 2.049(4); Ni—N, 2.091 (4)-2.156(5); Ga—O, 1.898(4) and 1.899(4); Ga—N, two at 1.991 (5); and Ga—C, 1.948(8)-1.971 (7) Å for the mer isomer.

Synthesis and Structural Systematics of First-Row Transition Metal Complexes with 2-[Bis(benzimidazol-2-ylmethyl)amino]ethanol

1987 ◽  
Vol 42 (10) ◽  
pp. 1307-1314 ◽  
Author(s):  
Kazuhiro Takahashi ◽  
Yuzo Nishida
Keyword(s):  
Transition Metal ◽  
Metal Ions ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Structural Parameters ◽  
Biological Systems ◽  
Tridentate Ligand ◽  
Crystal Data ◽  
Space Group ◽  
Distorted Octahedral

Abstract A nickel(II) complex with (bbimae) (= 2-[bis(benzimidazol-2-ylmethyl)amino]ethanol), [Ni(bbimae)(NCS)2] · H2O (1) and an oxovanadium(IV) complex, [VO(bbimae)(NCS)2] · dma (dma = N.N-dimethylacetamide) (2) have been prepared and their crystal structures determined by X-ray diffraction. Crystal data for 1 at 293 K: a = 13.334(2). b = 17.048(2), c = 10.3829(9) Å, space group P212121, Z = 4, and dcalcd = 1.41 gcm-3. Crystal data for 2 at 293 K: a = 14.099(2). b = 14.998(4), c = 14.051(2) Å, β = 107.634(9)°, space group P21/c, Z = 4, and dcalcd = 1.36 gcm-3. In the nickel(II) complex, (bbimae) functions as a tetradentate ligand, and the geometry around Ni(II) ion is best described as distorted octahedral. The structure is very similar to those of the correspond­ing Co(II) and Mn(II) complexes. In the case of 2, which is also distorted octahedral, (bbimae) is a tridentate ligand without the coordination of the alcohol group. The M-N (benzimidazole) distances are in the range of 1.95-2.18 Å, and also observed for other first-row transition metal complexes with (bbimae). and differ in the order V(IV) < Mn(II) > Co(II) > Ni(II) > Cu(II). consistent with effective ionic radii of the metal ions. Comparison of the structural parameters of these complexes with those of the metal ions in biological systems has supported the usefulness of the tripod-like ligands to synthesis model compounds for biological systems.

scholarly journals 1,3,5-Triaza-7-Phosphaadamantane (PTA) as a 31P NMR Probe for Organometallic Transition Metal Complexes in Solution

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1390 ◽  
Author(s):  
Ilya G. Shenderovich
Keyword(s):  
Chemical Shift ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Density Functional ◽  
Molecular Structures ◽  
Basis Sets ◽  
Functional Theory ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its 31P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this 31P chemical shift. This approach has been tested on a variety of the metals of groups 8–12 and molecular structures. General recommendations for appropriate basis sets are reported.

Übergangsmetallkomplexe mit Schwefelliganden, LXXIII. Diastereospezifische Dichlormethylierung schwefelreicher [RuII(SRR′)(PPh3)′S4]-Komplexe (SRR′ = einzähniger Thioether- oder Thiol-Ligand; ′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, LXXIII. Diastereospecific Dichloromethylation of Sulfur Rich [RuII(SRR′)(PPh3)′S4] Complexes (SRR′ = Monodentate Thioether or Thiol Ligand;′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-))

1991 ◽  
Vol 46 (12) ◽  
pp. 1585-1592 ◽  
Author(s):  
Dieter Sellmann ◽  
Peter Lechner ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Molecular Structures ◽  
X Ray ◽  
X Ray Crystallography ◽  
Thiol Ligand

Under exclusion of air the thioether and thiol complexes [Ru(SRR′)(PPh3)′S4′] (′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane (2—)) easily react with CHCl3 yielding [Ru(Cl)(PPh3)(′S4′—CHCl2)] in which one thiolato atom of the ′S4′ ligand is diastereospecifically dichloromethylated. In the presence of air, however, [RuIII(Cl)(PPh3)′S4′] is formed.The molecular structures of [Ru(Cl)(PPh3)(′S4′-CHCl2)] · 2CHCl3 and [RuIII(Cl)(PPh3)′buS4′] have been determined by X-ray crystallography. ′buS4′2- (= 1,2-bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2-)) is the t-butyl derivative of the ′S4′ ligand. Reasons for observed diastereospecifity of alkylation are discussed.

Coordination Chemistry of N,N′-Bis(diphenylphosphanylmethyl)- 2,3-dihydro-1H-perimidine – Lewis Acid-Base Complexes with the d10-Metals Nickel(0) and Gold(I)

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1299-1305 ◽  
Author(s):  
Sven Krieck ◽  
Daniel Schulze ◽  
Helmar Görls ◽  
Matthias Westerhausen
Keyword(s):  
Coordination Chemistry ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Lewis Acid ◽  
Nickel Complexes ◽  
Nickel Atom ◽  
Addition Reactions ◽  
Acid Base ◽  
Tetrahedral Environment

Abstract The addition reactions of N,N′-bis(diphenylphosphanylmethyl)-2,3-dihydro-1H-perimidine (1) with [(cod)2Ni] and [(Ph3P)AuCl] yield yellow [(1)Ni(η4-cod)] (2) and colorless [(1)(Ph3P)AuCl]·3MeOH (3), respectively. In these transition metal complexes of nickel(0) and gold(I) 1 acts as a bidentate chelating ligand. Crystal structures of [(1)Ni(η4-cod)]·3THF (2a) and of cosolvent-free [(1)Ni(η4-cod)] (2) reveal a distorted tetrahedral environment of the nickel atom. The gold(I) atom in 3 exhibits a very long Au-Cl bond of 296.2(1) pm. In contrast to the nickel complexes, compound 3 shows strong agostic interactions between gold(I) and a methylene fragment.

ChemInform Abstract: Transition Metal Complexes of the Novel Tridentate Di-2- pyridylmethanamine (dipa).

ChemInform ◽  
2010 ◽  
Vol 24 (4) ◽  
pp. no-no
Author(s):  
P. V. BERNHARDT ◽  
P. COMBA ◽  
A. MAHU-RICKENBACH ◽  
S. STEBLER ◽  
S. STEINER ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
The Novel
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