ChemInform Abstract: Low-Valent Molybdenum Carbonyl Complexes as an Entry to Octahedral MoI3L3 Complexes. Synthesis and X-Ray Molecular Structure of MoI3(THF)3.

ChemInform ◽  
1987 ◽  
Vol 18 (38) ◽  
Author(s):  
F. A. COTTON ◽  
R. POLI
2001 ◽  
Vol 66 (2) ◽  
pp. 382-396 ◽  
Author(s):  
Jan Čermák ◽  
Kateřina Auerová ◽  
Huong Thi Thu Nguyen ◽  
Vratislav Blechta ◽  
Pavel Vojtíšek ◽  
...  

Mixtures of isomers of (perfluoroalkyl)tetramethylcyclopenta-1,3-dienes (CH3)4C5H(CF2)nCF3 (n = 3, 5, 7, 9) were synthesized as precursors of new cyclopentadienyl ligands for organotransition metal catalysis in fluorous biphase media and characterized by combination of GC-MS and 13C NMR spectroscopy. Rhodium(III) chloro complexes [Rh{(CH3)4C5(CF2)nCF3}Cl2]2 and rhodium(I) carbonyl complexes [Rh{(CH3)4C5(CF2)nCF3}(CO)2] were prepared from the cyclopentadienes and molecular structure of [Rh{(CH3)4C5(CF2)5CF3}Cl2]2 was determined by X-ray diffraction. The ligands are electronically close to the unsubstituted cyclopentadienyl as shown by values of carbonyl stretching frequencies in the carbonyl complexes. Neither carbonyl frequencies nor NMR chemical shifts of the complexes are substantially affected by the length of the perfluoroalkyl chain.


2006 ◽  
Vol 84 (2) ◽  
pp. 330-336 ◽  
Author(s):  
Mozhgan Khorasani-Motlagh ◽  
Nasser Safari ◽  
Craig B Pamplin ◽  
Brian O Patrick ◽  
Brian R James

Oxidative addition of H2S to MoRu(CO)6(µ-dppm)2 (1) at ~20 °C in toluene yields an isolable complex formulated as Mo(CO)3(µ-SH)(µ-CO)(µ-dppm)2RuH(CO) (2) via the possible intermediate Mo(CO)3(µ-H)(µ-CO)(µ-dppm)2Ru(SH)(CO) (4) (dppm = Ph2PCH2PPh2) that is detectable at lower temperatures. Over 2 days, species 2 in toluene loses H2 (and CO) to yield the bridged-sulfide product, Mo(CO)2(µ-CO)(µ-S)(µ-dppm)2Ru(CO) (5) that is also formed directly from the reaction of 1 with elemental sulfur. The solid-state molecular structure of 5 is determined by X-ray crystallography. A further hydrido-sulfhydryl species, possibly Mo(CO)3(µ-SH)(µ-H)(µ-dppm)2Ru(CO)2 (3), is in equilibrium with 2 at ambient temperature.Key words: molybdenum, ruthenium, bis(diphenylphosphino)methane, hydrogen sulfide, hydrido-sulfhydryl species, carbonyl complexes, bridged-sulfide complex.


1981 ◽  
Vol 46 (1) ◽  
pp. 6-19 ◽  
Author(s):  
Viktor Kettman ◽  
Ján Garaj ◽  
Jaroslav Majer

The crystal and molecular structure of [Cr(S2CN(CH2)5)3].2 CHCl3 was found by the X-ray structural analysis method. The value R 0.090 was found for 1 131 observed independent reflections. The substance crystallizes in a space group of symmetry P212121 with the following unit cell dimensions: a = 0.8675 (6), b = 1.815(2), c = 2.155(3) nm. The experimentally observed crustal density was 1.48 Mgm-3 and the value calculated for Z = 4 was 1.51 Mgm-3. The CrS6 coordination polyhedron has the shape of a trigonally distorted octahedron, where the D3 symmetry is a approximately retained. The degree of trigonal distortion expressed as the projection of the chelate S-Cr-S angle onto the plane perpendicular to the C3 pseudo axis is Φ = 41.7° (Φ = 60° for an octahedron). The skeleton of the structure formed by the complex molecules contains channels filled with chloroform molecules. The specific type of complex-chloroform interaction consists of the formation of hydrogen bonds of the chloroform protons with the fully occupied pπ-orbitals of the sulphur atoms in the coordination polyhedra. The low stability and crystal decomposition can be explained by loss of chloroform from the channels.


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