N,S-Chelating Amino-ortho-carboranethiolate Complexes of Rhodium and Iridium: Synthesis and Reactivity. X-Ray Crystal Structures of (η4-C8H12)Rh[(NMe2CH2)SC2B10H10] and (CO)2Rh[(NMe2CH2)SC2B10H10]

1999 ◽  
Vol 64 (5) ◽  
pp. 883-894 ◽  
Author(s):  
Seung-Won Chung ◽  
Jaejung Ko ◽  
Kwonil Park ◽  
Sungil Cho ◽  
Sang Ook Kang
Keyword(s):  
Metal Atom ◽  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Carbonyl Complexes ◽  
Square Planar ◽  
Rhodium Atom ◽  
High Yields ◽  
New Compounds

The reaction of [M(μ-Cl)(cod)]2 (M = Rh, Ir; cod = cycloocta-1,5-diene) with two equivalents of the lithium ortho-carboranethiolate derivative LiCabN,S 2 [LiCabN,S = closo-2-(dimethylaminomethyl)-1-(lithiumthiolato)-ortho-carborane] produced the four-coordinated metallacyclic compounds, CabN,SM(cod) 3 (M = Rh 3a, Ir 3b), in which the metal atom was stabilized via intramolecular N,S-coordination. These new compounds have been isolated in high yields and characterized by IR and NMR spectroscopy. The structure consists of an amino-ortho-carboranethiolate fragment bonded to (cod)Rh(I) via nitrogen and sulfur, so as to give the metal a square-planar environment. Subsequent carbonylation reactions of 3a, 3b result in the quantitative formation of the corresponding (amino-ortho-carboranethiolato)(carbonyl)metal N,S-chelates CabN,SM(CO)2 4 (M = Rh 4a, Ir 4b). The metal carbonyl complexes 4a, 4b have been isolated and characterized by spectroscopic and compound 4a also by X-ray diffraction techniques. The molecular structure of 4a reveals that the rhodium atom is coordinated by nitrogen and sulfur atoms of the amino-ortho-carboranethiolate ligand, and two carbonyl ligands complete the coordination of the metal atom.

Intra- and intermolecular interactions in a series of chlorido-tricarbonyl-diazabutadienerhenium(I) complexes: structural and theoretical studies

2020 ◽  
Vol 76 (3) ◽  
pp. 417-426 ◽  
Author(s):  
Reza Kia ◽  
Azadeh Kalaghchi
Keyword(s):  
Intermolecular Interactions ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Lone Pair ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Covalent Interaction ◽  
Metal Carbonyl Complexes

A series of new chlorido-tricarbonylrhenium(I) complexes bearing alkyl-substituted diazabutadiene (DAB) ligands, namely N,N′-bis(2,4-dimethylbenzene)-1,4-diazabutadiene (L1), N,N′-bis(2,4-dimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L2), N,N′-bis(2,4,6-trimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L3) and N,N′-bis(2,6-diisopropylbenzene)-1,4-diazabutadiene (L4), were synthesized and investigated. The crystal structures have been fully characterized by X-ray diffraction and spectroscopic methods. Density functional theory, natural bond orbital and non-covalent interaction index methods have been used to study the optimized geometry in the gas phase and intra- and intermolecular interactions in the complexes, respectively. The most important studied interactions in these metal carbonyl complexes are n→π*, n→σ* and π→π*. Among complexes 1–4, only 2 shows interesting intermolecular n→π* interactions due to lp(C[triple-bond]O)...π* and lp(Cl)...π* (lp = lone pair) contacts.

Reaction of bromopentacarbonylrhenium(I) with ferrocenylcarbaldehyde thiosemicarbazones: the first X-ray diffraction studies of metal carbonyl complexes containing bidentate thiosemicarbazone ligands

2002 ◽  
Vol 656 (1-2) ◽  
pp. 1-10 ◽  
Author(s):  
Rosa Carballo ◽  
José S Casas ◽  
Emilia Garcı́a-Martı́nez ◽  
Gumersindo Pereiras-Gabián ◽  
Agustı́n Sánchez ◽  
...  
Keyword(s):  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Carbonyl Complexes

Zur Reaktivität von Natrium-bis-trimethylsilylamid gegenüber Metallcarbonylkomplexen mit Metall-Metall-Bindungen, I ER2-verbrückte Dicyano- und Diisonitril-octacarbonyl-dimanganate (E = Sn, Pb) / The Reactivity of Sodium Bis-trimethylsilylamide against Metal Carbonyl Complexes with Metal Metal Bonds, I ER2 Bridged Dicyano or Diisonitrile Octacarbonyl Dim anganates (E = Sn, Pb)

1986 ◽  
Vol 41 (5) ◽  
pp. 606-616 ◽  
Author(s):  
Matthias Moll ◽  
Helmut Behrens ◽  
Peter Merbach ◽  
Karl-Heinz Trümmer ◽  
Gerhard Thiele ◽  
...  
Keyword(s):  
Structure Analysis ◽  
Vibrational Spectra ◽  
Mass Spectra ◽  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
X Ray ◽  
Metal Carbonyl Complexes ◽  
Metal Metal ◽  
New Compounds ◽  
Metal Bonds

Abstract EPh2 bridged dicyano octacarbonyl dimetalates {Ph2E[Mn(CO)4CN]2}2- are formed by the reaction of bis(carbonyl-metalates) of tin and lead Ph2E[Mn(CO)5]2 with NaN(SiMe3)2. The new dicyano anions can be transformed with trialkyloxonium tetrafluoroborates [R′3O]BF4 or chlor-trimethylsilane and -germane into the corresponding diisonitrile complexes Ph2E[Mn(CO)4CNR′]2 (R′=Me, Et, SiMe3, GeMe3). In the case of Ph2E [Mn(CO)4CNR′]2 (R′=Me, Et; E=Sn, Pb) the two phenyl groups can be removed with dry hydrogenchloride to give Cl2E[Mn(CO)4CNR′]2.NMR and mass spectra are discussed. The vibrational spectra of the new compounds show cis-coordination of the Sn atoms and the cyano or isonitrile ligands in the carbonylmetalate fragments. This is confirmed by the X-ray structure analysis of Ph2Sn[Mn(CO)4CNMe]2 (space group P21/n).

The Crystal and Molecular Structure of Pentane-2,4-dionato-(2,3,5,6-tetrahepto-2,3-dicarbomethoxo[2.2.1]bicycloheptadiene)rhodium(I), Rh(C5H7O2) (C7H6(CO2CH3)2)

1975 ◽  
Vol 53 (18) ◽  
pp. 2707-2713 ◽  
Author(s):  
Debbie Allen ◽  
Colin James Lyne Lock ◽  
Graham Turner ◽  
John Powell
Keyword(s):  
Crystal And Molecular Structure ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Intensity Data ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Square Planar ◽  
Rhodium Atom

The crystal and molecular structures of pentane-2,4-dionato-(2,3,5,6-tetrahapto-2,3-dicarbomethoxo[2.2.1]bicycloheptadienerhodium(I), Rh(C5H7O2)(C7H6(CO2CH3)2), have been measured by single crystal X-ray diffraction. The orange crystals are monoclinic, space group P21/c, Z = 4, a = 9.245(4), b = 9.003(4), c = 21.680(15) Å, β = 113.41(5)°. The calculated and observed densities are 1.645 and 1.642(5) respectively. Intensity data were collected on a Syntex [Formula: see text] diffractometer and a full matrix least squares refinement on 3010 observed reflections leads to a conventional R = 0.0660. The structure can be considered as a roughly square planar arrangement of ligands around the rhodium atom composed of two β-ketoenolate oxygen atoms (Rh—O, 2.037(5) and 2.025(5) Å ) and the centers of the two ethylenic groups. The Rh—C distances for the olefin group attached to the two carbomethoxo groups, 2.117(8), 2.108(8) Å, appear to be slightly larger than those for the other olefinic group, 2.087(7), 2.082(6), and the corresponding C=C distances of 1.375(10) and 1.410(9) Å are different at the 95% confidence level.

Synthesis and X-ray structures of some metal carbonyl complexes containing dipyridylformamidine ligands

2003 ◽  
Vol 669 (1-2) ◽  
pp. 182-188 ◽  
Author(s):  
Hsiu-Chi Liang ◽  
Ying-Yann Wu ◽  
Fang-Chu Chang ◽  
Pang-Yen Yang ◽  
Jhy-Der Chen ◽  
...  
Keyword(s):  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
X Ray ◽  
Metal Carbonyl Complexes
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