A convenient synthesis of cis-Mo(CO)4L2 derivatives (L = Group 5a ligand) and a qualitative study of their thermal reactivity toward ligand dissociation

Darensbourg, Donald J.; Kump, Robin L.

doi:10.1021/ic50187a062

Cited by 276 publications

(185 citation statements)

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“…It should be highlighted the great coincidence between the isotopic pattern of calculated and experimental spectra for the three complexes. 21 The metal complexes 7-9 {[Mo(CO) 4 L 2 ] (L = 1, 2, 3)} were prepared from the complex [Mo(CO) 4 (pip) 2 ], which contains two labile piperidine ligands (Scheme 4), following the reported method for other [Mo(CO) 4 L 2 ] (L= neutral phosphine) complexes, 25 but with some significant differences in the reaction medium due to the ionic nature of ligands 1-3. Hence, 7-9 were synthesized using a synthetic method similar to that reported for [Mo(CO) 4 (TPPTS) 2 ], 26 but the experimental conditions had to be optimized in order to obtain pure products.…”

Section: Synthesis and Characterization Of Metallosurfactantsmentioning

confidence: 99%

Supramolecular Arrangement of Molybdenum Carbonyl Metallosurfactants with CO-Releasing Properties

Parera¹,

Marín-García²,

Pons

et al. 2016

Organometallics

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Two families of molybdenum carbonyl metallosurfactants, Mo(CO) 5 L and Mo(CO) 4 L 2 , were synthesized using the functionalized phosphines, Ph 2 P(CH 2 ) n SO 3 Na (n = 2, 6, 10) and characterized by the usual spectroscopic and spectrometric methods. The study of the supramolecular arrangements of these compounds in aqueous medium has been performed by surface tension, fluorescence, dynamic light scattering, cryo-TEM, and small angle X-ray scattering. All data points to the formation of medium and large vesicular structures with a membrane similar to the classical lipid bilayer, but it contains organometallic fragments instead of simple hydrophobic chains. Studies of CO releasing with these molybdenum carbonyl metallosurfactants have shown their viability as a promising CO releasing molecules.

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Section: Synthesis and Characterization Of Metallosurfactantsmentioning

confidence: 99%

Supramolecular Arrangement of Molybdenum Carbonyl Metallosurfactants with CO-Releasing Properties

Parera¹,

Marín-García²,

Pons

et al. 2016

Organometallics

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“…Darensbourg et al found that these complexes were synthesized by reacting [Mo(CO)6] with excess 2,2'-bipyridine (N-N) ligand in deoxygenated toluene at reflux (Scheme 17). Reaction times for the thermal synthesis of [Mo(CO)4(bipy)] complexes vary between 1.5 to 2.0 hours [81].…”

Section: M(co)4(bipy)mentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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KEYWORDSThe special interest attached to the chemistry of metal carbonyls arises from several causes. While quite distinct from the metal carbonyls in the organometallic compounds, they differ in physical properties (e.g., their volatility) from all other compounds of the transition metals. Chemically, they constitute a group of compounds in which the formal valency of the metal atoms is zero, and in this respect (apart, perhaps, from the ammoniates of the alkali metals) they are comparable only with the recently discovered compounds. As a class, the carbonyls are reactive compounds, and a number of new types of inorganic compounds have been discovered. In the concepts for new products, performance, product safety, and product economy criteria are equally important. They are taken into account already when the raw material base for a new industrial product development is defined. Since the discovery of nickel carbonyl by Mond and Langer in 1888, the carbonyls of the iron group and of chromium, molybdenum and tungsten have found important technical applications, e.g., in the Mond nickel process, and for the preparation of the metals in a state of subdivision and of purity suitable for powder metallurgy, for catalysts, etc. The reaction mechanism of the processes developed for producing the carbonyls technically has only recently received its interpretations. Within the space of review it is necessary to limit discussion to a few topics. Particular stress has accordingly laid upon (a) the chemical bonding in metal carbonyls, (b) importance of IR and NMR spectroscopy in characterization of metal carbonyls, (c) substitution reactions of G-VIb metal carbonyls, (d) kinetics and mechanism of substitution reactions in metal carbonyls, (e) substituted complexes of G-VIb metal carbonyl, (f) chelate complexes of G-VIb metal carbonyls, (g) uses of G-VIb metal carbonyl complexes and (h) studies done on G-VIb metal carbonyls.

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“…360 FTIR spectrometer. Dibenzo[d, f]-3,3',5,5'-tetratert-butyl-[1,3,2]dioxaphosphepin P-chloride [44] as well as the metal precursors PdCl 2 (cod), [45] and Mo(CO) 4 (pip) 2 [46] were prepared according to literature procedures. Also (c-C 5 H 9 ) 7 Si 8 O 13 Tl (A) and (c-C 5 H 9 ) 7 Si 7 O 9 (OH) 2 (OSiMePh 2 ) (B) were prepared according to literature procedures.…”

Section: Experimental Section General Remarksmentioning

confidence: 99%

Versatile Phosphite Ligands Based on Silsesquioxane Backbones

et al. 2004

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Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-dioxa-1,1'-biphenyl substituents. Both mono-and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting materials. The monophosphinite 1 and the monophosphite 2 are prepared from the thallium silsesquioxide derived from a completely condensed silsesquioxane framework (c-C 5 H 9 ) 7 Si 7 O 12 SiOTl. The diphosphite 3 is synthesized starting with the incompletely condensed monosilylated disilanol (c-C 5 H 9 ) 7 Si 7 O 9 (OSiMePh 2 )(OH) 2 . For monophosphite 2, the corresponding trans-[PtCl 2 (2)] complex 4 is characterized by NMR spectroscopy as well as by Xray crystallography, as the first example of a completely condensed oxo-functionalized silsesquioxane framework. The coordination of the bidentate ligand 3 towards Pd, Mo and Rh is studied, both by NMR spectroscopy as well as by X-ray crystallography.

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A convenient synthesis of cis-Mo(CO)4L2 derivatives (L = Group 5a ligand) and a qualitative study of their thermal reactivity toward ligand dissociation

Cited by 276 publications

References 11 publications

Supramolecular Arrangement of Molybdenum Carbonyl Metallosurfactants with CO-Releasing Properties

Supramolecular Arrangement of Molybdenum Carbonyl Metallosurfactants with CO-Releasing Properties

The chemistry of group-VIb metal carbonyls

Versatile Phosphite Ligands Based on Silsesquioxane Backbones

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