Highly diastereoselective formation and structural characterization of [2+2] cycloadducts from the phosphenium complexes Cp(OC)2M = P(Ph) (o-Tol) (M = Mo, W) and isocyanates

Malisch, Wolfgang; Hahner, Christoph; Grün, Klaus; Reising, Joachim; Goddard, Richard

doi:10.1016/0020-1693(95)04833-2

Cited by 15 publications

(5 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…After filtration, the solid was further washed with 20 mL of pentane, giving the product (PhNCS) 3 ( 8 ; 0.26 g, 72% yield). Spectroscopic data are consistent with those in the literature …”

Section: Methodssupporting

confidence: 90%

See 1 more Smart Citation

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

et al. 1998

View full text Add to dashboard Cite

Treatment of Cp(PPh 3 )[P(OMe) 3 ]RuCtCPh (2; Cp ) η 5 -C 5 H 5 ) with PhNdCdS at room temperature affords the [2 + 2] cycloaddition product Cp(PPh 3 )[P(OMe) 3 ]RuCdC(Ph)C-(dNPh)S (3a), containing a four-membered ring, and the neutral vinylidene phosphonate complex Cp(PPh 3 )[P(dO)(OMe) 2 ]RudCdC(Ph)C(SH)dNPh (4a) in a 9:1 ratio. Formation of 4a results from an Arbuzov-like dealkylation reaction possibly after addition of PhNdCdS.The same reaction at 40 °C affords a higher yield of 4a and Cp(PPh 3 )[P(OMe) 3 ]RuCdC-(Ph)C(dS)N(R)C(dNR)S (5a; R ) Ph) which results from addition of a second isothiocyanate to the four-membered ring of 3a. The reaction of 2 with PhCH 2 NdCdS at room temperature directly affords the six-membered-ring product 5b (R ) CH 2 Ph). Trimerization of phenyl isothiocyanate is catalyzed by Cp(dppe)RuCtCPh (1′; dppe ) Ph 2 PCH 2 CH 2 PPh 2 ) in refluxing CH 2 Cl 2 . This catalytic reaction proceeds through a pathway in which the first two steps are the same as those observed in the reaction of 2a. An attempt to purify the precursor of the trimerization product gave the cocrystallization of 1′ and (PhNCS) 3 (8). The structures of 3a, 4a, 5b, and the cocrystallization product of 1′ and 8 have been determined by singlecrystal X-ray diffraction analysis.

show abstract

Section: Methodssupporting

confidence: 90%

“…A similar process has been proposed for the first stage of the reaction of alkynes with CS 2 . The reaction of phosphenium complexes with isocyanates leading to [2 + 2] addition via the NC bond to give four-membered phosphametallacycles has been reported …”

Section: Resultsmentioning

confidence: 61%

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

et al. 1998

View full text Add to dashboard Cite

show abstract

“…A similar process has been proposed in the first stage of the reaction of alkyne with CS 2 , giving a 2 H -thiete-2-thione intermediate which was characterized spectroscopically . Reaction of phosphenium complexes with isocyanates via a [2 + 2] addition of the NC bond to give the four-membered phosphametallacycles has also been reported …”

Section: Resultssupporting

confidence: 53%

Reactions of Ruthenium Acetylide Complexes with EtO₂CNCS: Alkylation of the Thione with Dichloromethane

et al. 2003

View full text Add to dashboard Cite

Treatment of the ruthenium acetylide complexes [M]C⋮CPh (1a, [M] = [Ru] = Cp(Ph2PCH2CH2PPh2)Ru; 1b, [M] = [Ru‘] = Cp(PPh3)[P(OMe)3]Ru) with 1.1 equiv of EtO2CNCS results in [2 + 2] cycloadditions yielding the four-membered-ring 2-iminothiete products 2a,b, respectively. Isomerization of complex 2a results in formation of 3a containing the six-membered-ring oxazinethione ligand. Alkylation of complex 3a by CH2Cl2 takes place at the thione sulfur to give 4a, which loses ethyl chloride, yielding the new six-membered-ring [1,3]-oxazin-2-one complex 5a. Further alkylation of 3a by the chloromethyl group of 5a affords the dinuclear complex 6a with two oxazin-2-one ligands bridged by a methylene group. Structures of 2b, 3a, 5a and 6a have been determined by single-crystal X-ray diffraction analysis.

show abstract

“…described the chemo-and regioselective cycloaddition of Pure 4a, b is isolated by column chromatography in good the phosphenium complexes Cp(OC) 2 MϭP(R) (o-Tol) yield as a deep red and orange crystalline powder, respec-(M ϭ Mo, W; R ϭ Ph, o-Tol) to organic isocyanates yieldtively. The structure is proved by the 31 P-NMR spectra, ing the [2 ϩ 2] cycloaddition products Cp(OC) 2 MϪP(R) (o-with signals at δ ϭ 39.7 (4a) and 11.9 (4b) and 1 J(WP) Tol)ϪC(ϭO)ϪNEt(MϪN) [3] . couplings of 213.8 (4a) and 230.2 Hz (4b) appearing in the We now report about the cycloaddition reaction between characteristic range of four-membered phosphametallathe diorganophosphenium complexes Cp(OC) 2 Wϭ cycles [3] .…”

Section: Introduction Resultsmentioning

confidence: 98%

“…The structure is proved by the 31 P-NMR spectra, ing the [2 ϩ 2] cycloaddition products Cp(OC) 2 MϪP(R) (o-with signals at δ ϭ 39.7 (4a) and 11.9 (4b) and 1 J(WP) Tol)ϪC(ϭO)ϪNEt(MϪN) [3] . couplings of 213.8 (4a) and 230.2 Hz (4b) appearing in the We now report about the cycloaddition reaction between characteristic range of four-membered phosphametallathe diorganophosphenium complexes Cp(OC) 2 Wϭ cycles [3] . The signal of the P-bonded sp 2 -carbon atom of 4b P(tBu)(R) [R ϭ tBu (2a), Ph (2b)] bearing one or two tertis observed in the 13 C-NMR spectrum as a doublet in the butyl ligands at the phosphorus atom and EtNCS affordtypical low-field region at δ ϭ 183.0 with a 1 J(PC) coupling ing, in addition to the expected cycloadduct, an unusual of 49.6 Hz.…”

Section: Introduction Resultsmentioning

confidence: 98%

Reaction of the Phosphenium Complexes Cp(OC)2W=P(tBu)(R) with Ethyl Isothiocyanate: Unprecedented Formation of the Phosphametalla Spiro Compound {Cp(OC)2W–P(tBu)(R)–N(Et)–Ca[N(Et)–(CH)–N(Et)CbH2]–S(W–S)(Ca–Cb)}Cl (R =tBu, Ph)

Malisch¹,

Baky²,

Grün³

et al. 1998

Eur. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

Reaction of the phosphenium complexes Cp(OC)2W=P(tBu)(R) [R = tBu (2a), Ph (2b)] with ethyl isothiocyanate (3) leads to the formation of the phosphametallacycles Cp(OC)2W–P(tBu)(R)–C(=NEt)–S(W–S) (4a, b) by [2 + 2] cycloaddition. In contrast, the “in situ” reaction of 2a, b, generated from Cp(OC)2[H(tBu)(R)P]W–Cl (1a, b) with DBU in the presence of 3 leads to the spirocyclic phosphorus metal compounds {Cp(OC)2W–P(tBu)(R)–N(Et)–Ca[N(Et)–(CH)–N(Et)CbH2]–S(W–S)(Ca–Cb)}Cl (6a, b). The structure of 6a has been proved by X‐ray analysis.

show abstract

Highly diastereoselective formation and structural characterization of [2+2] cycloadducts from the phosphenium complexes Cp(OC)2M = P(Ph) (o-Tol) (M = Mo, W) and isocyanates

Cited by 15 publications

References 3 publications

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

Reactions of Ruthenium Acetylide Complexes with EtO₂CNCS: Alkylation of the Thione with Dichloromethane

Reaction of the Phosphenium Complexes Cp(OC)2W=P(tBu)(R) with Ethyl Isothiocyanate: Unprecedented Formation of the Phosphametalla Spiro Compound {Cp(OC)2W–P(tBu)(R)–N(Et)–Ca[N(Et)–(CH)–N(Et)CbH2]–S(W–S)(Ca–Cb)}Cl (R =tBu, Ph)

Contact Info

Product

Resources

About

Highly diastereoselective formation and structural characterization of [2+2] cycloadducts from the phosphenium complexes Cp(OC)2M = P(Ph) (o-Tol) (M = Mo, W) and isocyanates

Cited by 15 publications

References 3 publications

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

Reactions of Ruthenium Acetylide Complexes with EtO2CNCS: Alkylation of the Thione with Dichloromethane

Reaction of the Phosphenium Complexes Cp(OC)2W=P(tBu)(R) with Ethyl Isothiocyanate: Unprecedented Formation of the Phosphametalla Spiro Compound {Cp(OC)2W–P(tBu)(R)–N(Et)–Ca[N(Et)–(CH)–N(Et)CbH2]–S(W–S)(Ca–Cb)}Cl (R =tBu, Ph)

Contact Info

Product

Resources

About

Reactions of Ruthenium Acetylide Complexes with EtO₂CNCS: Alkylation of the Thione with Dichloromethane