Carbonyl halides of the Group VIII transition metals. VI. Compounds of palladium(I)

1973 ◽  
Vol 26 (12) ◽  
pp. 2607 ◽  
Author(s):  
R Colton ◽  
RH Farthing ◽  
MJ McCormick
Keyword(s):  
Carbon Monoxide ◽  
Transition Metals ◽  
Acid Solution ◽  
Direct Interaction ◽  
Group Viii ◽  
Physical Measurements ◽  
Rubidium Salt ◽  
Hydrohalic Acid

The carbonyl halides Pd(CO)Cl and Pd(CO)Br have been prepared by the action of carbon monoxide on palladium(II) halides in aqueous hydrohalic acid solution. In addition, the caesium salts CsPd(CO)Cl2 and CsPd(CO)Br2, and the rubidium salt RbPd(CO)Cl2, were also isolated. The corresponding iodo complexes could not be prepared. ��� By direct interaction of the carbonyl halides with bis(diphenylarsino)methane (dam) the compounds [Pd(dam)X]2 (X = Cl, Br) were prepared. The formulation of all these complexes as compounds of palladium(I) was confirmed on the basis of various physical measurements.

Carbonyl halides of the Group VIII transition metals. V. Halocarbonyl derivatives of ruthenium(III) and ruthenium(II)

1971 ◽  
Vol 24 (5) ◽  
pp. 903 ◽  
Author(s):  
R Colton ◽  
RH Farthing
Keyword(s):  
Carbon Monoxide ◽  
Transition Metals ◽  
Formic Acid ◽  
Direct Reaction ◽  
Group Viii ◽  
Reaction Solution ◽  
Derivatives Of ◽  
Hydrohalic Acid

Formic acid in the appropriate hydrohalic acid both carbonylates and reduces ruthenium trihalides, but the nature of the products isolated depends upon the identity of the halogen. In the chloro system the first product is the pentachloro-carbonylruthenate(III) ion, [Ru(CO)Cl5]2-, and this is then reduced to the tetra- chlorocarbonylaquoruthenate(II) ion, [Ru(CO)(H2O)Cl4]2-. More prolonged reaction gives [Ru(CO)2Cl4]2- and the ultimate product is [Ru(CO)3Cl3]-. ��� In the bromo system there was no evidence for the formation of an aquo-ruthenium(II) species and the iodo system was even more simple as only [Ru(CO)2I4]2- and [Ru(CO)3I3]- were observed. ��� The direct reaction between carbon monoxide and RuX3 in methanol produces compounds of the type Ru(CO)X3 (X = Cl, Br) and the corresponding anions [Ru(CO)X5]- have been isolated and characterized. ��� In all cases the halocarbonyl anions could be isolated by the addition of suitable cations to the solutions. In most cases the parent halocarbonyls themselves were isolated by evaporation of the reaction solution without the addition of cations.

Carbonyl halides of the Group VIII transition metals. IV. Halocarbonyls and halocarbonyl anions of rhodium(III) and rhodium(I)

1970 ◽  
Vol 23 (7) ◽  
pp. 1351 ◽  
Author(s):  
R Colton ◽  
RH Farthing ◽  
JE Knapp
Keyword(s):  
Infrared Spectroscopy ◽  
Transition Metals ◽  
Formic Acid ◽  
Oxidation State ◽  
Intermediate Formation ◽  
Acid Mixture ◽  
Group Viii ◽  
Subsequent Reduction ◽  
Reaction Proceeds ◽  
Hydrohalic Acid

Both rhodium trichloride and tribromide are easily carbonylated and subsequently reduced by refluxing formic acid-hydrohalic acid mixture to give almost quantitative yields of the rhodium(1) halocarbonyl anions [Rh(CO)2X2]- (X = Cl,Br). It has been shown that the reaction proceeds by the intermediate formation of the rhodium(111) halocarbonyl anions [Rh(CO)X5]2- followed by slow reduction to the rhodium(1) complexes. Evaporation of the respective solutions leads to almost quantitative recovery of the new rhodium(111) halocarbonyls Rh(CO)X3 and the well known rhodium(1) compounds [Rh(C0)2X]2. Iododicarbonylrhodium(1) could not be isolated by this method and in fact the only products which could be isolated were triiodocarbonylrhodium(111), Rh(CO)I3, and its corresponding anion; this shows that although the carbonylation reaction had occurred the subsequent reduction did not proceed. In solution the rhodium(1) complexes [Rh(C0)2X2]- oxidize to give [Rh(CO)X5]2-. Caesium salts of these rhodium(111) anions are readily isolated, but addition of caesium salts to the rhodium(1) solutions did not give the expected Cs[Rh(CO)2X2] but instead the octahedral complexes Cs2[Rh(C0)2(H2O)X3]. All of these changes in composition and oxidation state have been followed in solution, as well as in the isolated solid products, by infrared spectroscopy.

Carbonyl halides of the Group VI transition metals. XVI. Reactions of Bis(diphenylphosphino)methane with Diiodotetracarbonyltungsten(II)

1969 ◽  
Vol 22 (12) ◽  
pp. 2535 ◽  
Author(s):  
R Colton ◽  
CJ Rix
Keyword(s):  
Carbon Monoxide ◽  
Transition Metals ◽  
Molecular Species ◽  
Direct Interaction ◽  
Ionic Species ◽  
Reaction Scheme ◽  
Simple System ◽  
Tricarbonyl Complex ◽  
Group Vi ◽  
Unusual Type

Compounds of the general formulae W(CO)3dpmI2 and W(CO)2(dpm)2I2 [dpm = bis(diphenylphosphino)methane] have been prepared by direct interaction of the ligand with diiodotetracarbonyltungsten(II). However, this apparently simple system is complicated by the existence of two isomers of the tricarbonyl complex and three isomeric forms of the dicarbonyl. The various isomers have been separated and characterized individually and the interconversions between all the complexes have been investigated. The overall reaction scheme contains a partial carbon monoxide carrying system and an example of an unusual type of isomerism: �������������������� W(CO)2(dpm)2I2 → [W(CO)2(dpm)2I]I that is, isomerism of a molecular species to an ionic species.

Carbonyl halides of the Group VI transition metals. V. Carbon monoxide carriers and some sulphur and nitrogen derivatives of molybdenum halocarbonyls

1968 ◽  
Vol 21 (1) ◽  
pp. 15 ◽  
Author(s):  
R Colton ◽  
GR Scollary ◽  
IB Tomkins
Keyword(s):  
Carbon Monoxide ◽  
Transition Metals ◽  
Direct Interaction ◽  
Group Vi ◽  
Derivatives Of

The blue compounds MX2(CO)2(Ph3P)2 (M = Mo and W, X = Cl and Br) have been shown to absorb carbon monoxide very readily indeed to form the corresponding tricarbonyls, and as reported earlier, the tricarbonyls may be easily converted into the dicarbonyls. The dicarbonyl is therefore a carbon monoxide carrier. The compounds Mo(CO)3 dtc2 and Mo(CO)2 dtc2 (dtc = diethyldithiocarbamate) also represent a carbon monoxide carrying system, but in this case both compounds are rather unstable. The compounds MoX2(CO)2 btp2 (btp = N-n-butylthiopicolinamide; X = Cl, Br) have been prepared by direct interaction of the ligand and the appropriate halocarbonyl. Although these compounds are believed to be monomeric they do not absorb carbon monoxide.

Carbonyl halides of the Group VI transition metals. XIX. Iodocarbonyl complexes of molybdenum and tungsten with Bis(diphenylarsino)methane

1970 ◽  
Vol 23 (3) ◽  
pp. 441 ◽  
Author(s):  
R Colton ◽  
CJ Rix
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Carbon Monoxide ◽  
Magnetic Resonance ◽  
Transition Metals ◽  
Direct Interaction ◽  
Acetone Solution ◽  
Group Vi ◽  
First Time ◽  
And Tungsten ◽  
Nuclear Magnetic

Complexes of the general formulae M(CO)3(dam)I2, M(CO)3(dam)2I2, and M(CO)2(dam)2I2 have been prepared and characterized [M = Mo, W; dam = bis(diphenylarsino)methane]. All of the compounds are diamagnetic and non-electrolytes in acetone solution. The tungsten derivatives were prepared by direct interaction of dam with diiodotetracarbonyltungsten(11), but the molybdenum analogues were obtained by iodine oxidation of the zero-valent complex Mo(CO)4(dam)2 whose preparation is reported for the first time in this paper. The bis(dam)tricarbonyl complexes, M(C0)3(dam)2I2, are unstable in solution giving M(CO)2(dam)I2 and free dam in equilibrium with undissociated complex. The bis(dam)tricarbonyl complexes also readily lose carbon monoxide, especially in the case of molybdenum, to give M(CO)z(dam)2I2. These dicarbonyl complexes readily absorb carbon monoxide to re-form the tricarbonyl complexes to give a reversible carbon monoxide carrying system. Overall, these systems may be represented by the general equations : M(CO)3(dam)I2 + dam ↔ M(CO)3(dam)2I2 + CO These equilibria have been studied using both infrared and nuclear magnetic resonance techniques.

Carbonyl halides of the Group VII transition metals. I. Halocarbonyls and halocarbonyl anions of rhenium(I)

1972 ◽  
Vol 25 (1) ◽  
pp. 9 ◽  
Author(s):  
R Colton ◽  
JE Knapp
Keyword(s):  
Transition Metals ◽  
Acid Solution ◽  
Formic Acid ◽  
Spectral Studies ◽  
Efficient Production ◽  
Formic Acid Solution ◽  
Visible Absorption ◽  
Initial Reduction ◽  
Intermediate Oxidation ◽  
Hydrohalic Acid

The rhenium(1) halocarbonyls Re(CO)5X (X = Cl, Br, I) may be readily prepared by refluxing a solution of the free hexahalorhenate(1V) acid in hydrohalic acid with formic acid. Visible absorption spectral studies indicate that formation of the halocarbonyls takes place following an initial reduction to rhenium(111), but no halocarbonyls of this intermediate oxidation state were isolated. The concentration of rhenium, as well as the relative amounts of hydrohalic and formic acids in the reaction mixture, are important factors for efficient production of the halocarbonyls. If the halocarbonyls are refluxed in formic acid containing a decreased proportion of hydrohalic acid, decarbonylation occurs giving the halocarbonyl anions [Re(CO)4X]2- which can be isolated as their caesium salts or as the parent halocarbonyls [Re(CO)4X]2. Continued refluxing of the formic acid solution causes still further decarbonylation giving the halocarbonyl anions [Re(CO)3X3]2- (X = Cl, Br) which may also be isolated as their caesium salts. Alternatively, evaporation to dryness of these solutions without addition of cations gives the new rhenium(1) halocarbonyl aquo complexes Re(CO)3(H2O)2X (X = Cl, Br). In the case of the iodo system, decarbonylation did not proceed to the tricarbonyl stage.

Approximation of adsorption heats of carbon monoxide on transition metals by means of an empirical model

1983 ◽  
Vol 48 (10) ◽  
pp. 2735-2739
Author(s):  
Jiří Fusek ◽  
Oldřich Štrouf ◽  
Karel Kuchynka
Keyword(s):  
Carbon Monoxide ◽  
Heat Capacity ◽  
Transition Metals ◽  
Molar Heat Capacity ◽  
Metal Adsorption ◽  
Heat Of Fusion ◽  
Class Structure ◽  
Fundamental Parameters ◽  
Adsorption Heats ◽  
Pauling Electronegativity

The class structure of transition metals chemisorbing carbon monoxide was determined by expressing the following fundamental parameters in the form of functions: The molar heat capacity, the 1st and 2nd ionization energy, the heat of fusion, Pauling electronegativity, the electric conductivity, Debye temperature, the atomic volume of metal. Adsorption heats have been predicted for twelve transition metals.

Butterfly Cluster Complexes of the Group VIII Transition Metals

2007 ◽  
pp. 437-525 ◽  
Author(s):  
Enrico Sappa ◽  
Antonio Tiripicchio ◽  
Arthur J. Carty ◽  
Gerald E. Toogood
Keyword(s):  
Transition Metals ◽  
Group Viii ◽  
Cluster Complexes ◽  
Butterfly Cluster
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