Reaction of pentacarbonyl(η2-bis(trimethylsilyl)ethyne)tungsten(0) with tricyclohexylphosphine: X-ray structure of pentacarbonyltricyclohexylphosphinetungsten(0)

Demircan, Oktay; Özkâr, Saim; Ülkü, D.; Yıldırım, Leyla Tatar

doi:10.1016/j.jorganchem.2003.08.032

Cited by 8 publications

(7 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The broad band appeared at 1872, 1865, and 1875 cm −1 and the sharper band at 2004, 2009, and 2007 for 5 , 6 , and 7 , respectively. These infrared features closely resemble previously reported spectra for cis -M(CO) 4 (PCy 3 ) 2 compounds, which led us to suspect that a ligand redistribution reaction had occurred, eq . This hypothesis was verified by the lack of reactivity of these complexes with added CO.…”

Section: Resultssupporting

confidence: 87%

“… The 13 C NMR spectra of 5 and 6 each exhibit six different peaks for the cyclohexyl groups, indicating the diastereotopic effects observed in 3 (described above) are carried through to the metal analogues. The resonance due to carbon C1 is shifted 7 ppm farther downfield, a trend which has also been reported for M(CO) 4 (PCy 3 ) 2 compounds . Similarly, the tertiary carbon attached directly to phosphorus in 7 is shifted ∼7 ppm downfield.…”

Section: Resultssupporting

confidence: 75%

See 1 more Smart Citation

Synthesis and Structure of Molybdenum and Tungsten Bisphosphine Carbonyl Dimers

Brayton

Heinekey

2008

Organometallics

View full text Add to dashboard Cite

The synthesis of two bisphosphine ligands (R2P)2C6H4 with a para-disubstituted phenyl moiety is described (R = Cy (3), i-Pr (4)). Solutions of M(CO)3(C7H8) (C7H8 = η6-cycloheptatriene, M = Mo and W) and 3 or 4 were reacted under CO affording dimeric compounds of the general formula [M2(CO)8((R2P)2C6H4)2] (M = W, R = Cy (5); M = Mo, R = Cy (6); and M = W, R = i-Pr (7)). When the same reactions are carried out in the presence of H2, similar W−H2 analogues of the general formula [W2(CO)6((R2P)2C6H4)2(H2)2], R = Cy (8), R = i-Pr (9), can be observed by 1H and 31P NMR spectroscopy. Compounds 8 and 9 are not isolable, due to facile ligand redistribution forming 5 and 7, respectively.

show abstract

Section: Resultssupporting

confidence: 87%

Section: Resultssupporting

confidence: 75%

Synthesis and Structure of Molybdenum and Tungsten Bisphosphine Carbonyl Dimers

Brayton

Heinekey

2008

Organometallics

View full text Add to dashboard Cite

show abstract

“…The pentacarbonyl(η 2 -bis(trimethylsilyl)ethyne)tungsten(0), W(CO)5(η 2 -btmse), reacts with tricyclohexylphosphine, PCy3, to yield W(CO)5(PCy3) and W(CO)4(PCy3)2. The former complex is the alkyne substitution product, while the latter one is formed from the conversion of its labile cis-isomer, which is generated by further reaction of the CO substitution product, cis-W(CO)4(η 2 -btmse)(PCy3), with a second PCy3 molecule (Scheme 37) [161].…”

Section: Scheme 36mentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

View full text Add to dashboard Cite

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.

show abstract

“…The structure ( Figure 4) has the expected octahedral arrangement of ligands with phenop trans to a single carbonyl and the remaining CO donors coplanar. The W-P bond length of 2.6292(10) Å is long for this type of complex when compared to related structurally characterised derivatives such as [W(CO) 5 (PMe 3 )] [2.516(2) Å], [15] [W(CO) 5 [17] but is shorter than the value of 2.686 Å observed in the tri-tertbutylphosphane analogue. [18] As expected the W-C bond length to the carbonyl carbon trans to the phosphane is the shortest at 1.985(5) Å compared to the other W-C bond lengths which are all longer than 2.040 Å.…”

Section: Syntheses and Structure Of The Metal Complexes Of Phenopmentioning

confidence: 89%

Metal Complexes of a Structurally Embellished Phosphinane Ligand: An Assessment of Stereoelectronic Effects

et al. 2011

View full text Add to dashboard Cite

The stereoelectronic features of the pentacyclic phosphane (1S,4R,4aS,5aR,6R,9S,9aS,10aR)‐4,6,11,11,12,12‐hexamethyl‐10‐phenyldodecahydro‐1,4:6,9‐dimethanophenoxaphosphinine (phenop) have been explored through a range of empirical methods including single‐crystal X‐ray structure determinations of the sulfide derivative phenopS (1), the selenide phenopSe (2), [Fe(CO)4(κ1‐phenop)] (3), [W(CO)5(κ1‐phenop)] (4) and trans‐[Rh(κ1‐phenop)(CO)Cl] (5). Cone angles derived from the structural data range from 164–203° with the smaller values being observed for the compounds possessing a phenyl group that is orthogonal to the P–Z bond and the larger values for the compounds expressing a parallel phenyl ring orientation. The cone angle data suggest a moderately bulky phosphane comparable, in steric terms, to PCy3. This is further borne out on inspection of the M–P bond lengths which tend towards the longer end of the known scale. Some flexibility is observed in the central ring which approximates to a boat conformation at one extreme and an envelope at the other depending on the nature of the P‐substituent. The electronic properties of κ1‐phenop have been assessed using a combination of infrared and NMR spectroscopy. The absolute value of the one‐bond coupling constants 1JP‐Se and 1JP‐Rh are very close to those reported for PPh3, suggesting a close analogy between κ1‐phenop and the well known triphenylphosphane. In addition, relevant υ(CO) stretches in the IR spectra of the metal carbonyl complexes also closely mimic those for the analogous complexes containing PPh3. These conclusions are supported by molecular electrostatic potential calculations at the DFT level which place phenop close to PPh3 in terms of lone pair availability.

show abstract

Reaction of pentacarbonyl(η2-bis(trimethylsilyl)ethyne)tungsten(0) with tricyclohexylphosphine: X-ray structure of pentacarbonyltricyclohexylphosphinetungsten(0)

Cited by 8 publications

References 28 publications

Synthesis and Structure of Molybdenum and Tungsten Bisphosphine Carbonyl Dimers

Synthesis and Structure of Molybdenum and Tungsten Bisphosphine Carbonyl Dimers

The chemistry of group-VIb metal carbonyls

Metal Complexes of a Structurally Embellished Phosphinane Ligand: An Assessment of Stereoelectronic Effects

Contact Info

Product

Resources

About