Synthesis of new (cyclopentadienyl)rutheniumphosphine complexes with hemilabile ether-phosphines. The X-ray structure of (η5-C5H5)RuCl(Ph2PCH2CH2OCH3)2

Klerk-Engels, Barbara de; Groen, J.H.; Vrieze, K.; Möckel, A.; Lindner, Ekkehard

doi:10.1016/s0020-1693(00)85318-9

Cited by 22 publications

(7 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this mechanism, the formation of the neutral complexes 2 and 2 ‘ only arises through the competition between the chloride anion and the keto oxygen atom, in coordinating at the ruthenium center. The first mechanism appears unlikely when the conditions of the reaction are compared to the conditions where the straightforward substitution of triphenylphosphine in 1 by functional ether phosphines is achieved .…”

Section: Resultsmentioning

confidence: 99%

“…The first mechanism appears unlikely when the conditions of the reaction are compared to the conditions where the straightforward substitution of triphenylphosphine in 1 by functional ether phosphines is achieved . Of further interest, the chloride ligand in 1 is already known to be substituted in methanol by phosphorus ligands to afford cationic tris(phosphine) complexes, despite the fact that formation of the species [Ru(η 5 -C 5 H 5 )(PPh 3 ) 3 ] + is believed to be sterically hindered .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (S_Ru,R_C/R_Ru,S_C)- [Ru(η⁵-C₉H₇)(PPh₃){η²(P,O)-Ph₂PCH(Me)C(Bu^t)O}][PF₆] and (S_Ru,R_C/R_Ru,S_C<

Crochet¹,

Demerseman²,

Vallejo³

et al. 1997

Organometallics

40
1
25
0

View full text Add to dashboard Cite

The reaction of β-keto phosphines Ph2PCH(R‘)C(O)R (a, R = But, R‘ = H; b, R = Ph, R‘ = H; c, R = But, R‘ = Me) with [RuCl(η5-C n H m )(PPh3)2] complexes (1, C n H m = cyclopentadienyl; 1 ‘, C n H m = indenyl) affords neutral [RuCl(η5-C n H m )(PPh3){η1(P)-keto phosphine}] (2a,b and 2 ‘ a). Cationic derivatives, [Ru(η5-C n H m )(PPh3){η2(P,O)-keto phosphine}][PF6] (3a,b and 3 ‘ a − c), are obtained by the reactions of complexes 1 and 1 ‘ with the keto phosphines in the presence of NH4PF6. Complex 3 ‘ c is diastereoselectively obtained as the S Ru ,R C /R Ru ,S C enantiomeric pair, as shown by an X-ray crystal structure analysis. Owing to the hemilabile ability of the keto phosphine ligand, complexes 3a and 3 ‘ a easily react with 1,1-diphenyl-2-propyn-1-ol to yield the allenylidene complexes [Ru(CCCPh2)(η5-C n H m )(PPh3){η1(P)-Ph2PCH2C(O)But}][PF6] (5a and 5 ‘ a, respectively). Treatment of complexes 3a and 3 ‘ a with K2CO3 in methanol leads to the deprotonation of the coordinated keto phosphine to give the neutral phosphino enolate derivatives [Ru(η5-C n H m )(PPh3){η2(P,O)-Ph2PCHC(But)O}] (6a and 6 ‘ a, respectively). In contrast, allenylidene complexes 5a and 5 ‘ a react with K2CO3 or KOH in methanol to afford the alkynyl complexes [Ru{C⋮CC(OMe)Ph2}(η5-C n H m )(PPh3){η1(P)-Ph2PCH2C(O)But}] (7a and 7 ‘ a), which are formed through the nucleophilic addition of the methoxy group to the Cγ atom of the allenylidene chain. Similarly, the ethoxy alkynyl derivative 8a is obtained by the reaction of 5a with KOH in ethanol. Under mild basic conditions (K2CO3/THF) complexes 5a and 5 ‘ a are deprotonated, resulting in conversion into the neutral and 9 ‘ a, respectively) through the generation of a novel phosphametallacyclobutane ring and in accord with a diastereoselective process. The molecular structure of 9 ‘ a, determined by an X-ray crystal structure analysis, discloses a S Ru ,R C /R Ru ,S C configuration and shows a nearly planar Ru−P(2)−C(2B)−C(1) ring bearing an almost linear η1(C)-coordinated allenyl group (C(1)−C(2A)−(3A) = 169.6(8)°). The formation of the four-membered ring probably takes place in a putative intermediate arising from the deprotonation of the η1(P)-keto phosphine ligand in 5a and 5 ‘ a. The subsequent intramolecular carbon−carbon bond formation between the allenylidene group and the nucleophilic η1(P)-phosphino enolate ligands is geometrically constrained to occur at the electrophilic Cα site of the allenylidene ligand, and the ruthenium fragment efficiently directs the configuration of the new stereogenic carbon atom in the resulting metallacycle ring.

show abstract

Section: Resultsmentioning
confidence: 99%

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (S_Ru,R_C/R_Ru,S_C)- [Ru(η⁵-C₉H₇)(PPh₃){η²(P,O)-Ph₂PCH(Me)C(Bu^t)O}][PF₆] and (S_Ru,R_C/R_Ru,S_C<
Crochet¹,
Demerseman²,
Vallejo³
et al. 1997
Organometallics
40
1
25
0
View full text Add to dashboard Cite

show abstract

“…For five-membered rings, an additional 20Ϫ30 ppm downfield shift is typical. [27,28] The 31 P NMR spectra of 5b, 5c and 5e exhibit this feature, an example is shown in Figure 6. The NO stretching frequency was found in the typical range for cationic ether [29] or thioether [6,30,31] complexes of the general formula [CpRe(NO)(PR 3 )(L)] ϩ .…”

Section: Full Papermentioning
confidence: 86%

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands
Dilsky
¹
,
Schenk
²

2004
Eur J Inorg Chem
10
1
2
0
View full text Add to dashboard Cite

The syntheses and some typical reactions of diastereomeric rhenium complexes [CpRe(NO)(CO){P(Ph)(R)(R′)}]BF4 (R = Me, Ph; R′ = 2‐C6H4OMe, CH2C4H3S, CH2C4H7O) (3a−e) are described. Reduction of the carbonyl ligand with NaBH4 in THF gave the corresponding methyl complexes [CpRe(NO){P(Ph)(R)(R′)}(CH3)] (4a−e). Acid treatment of the methyl complexes leads to liberation of methane and coordination of the additional donor site of the potentially bidentate phosphane ligand. Of the chelate complexes 5a−e, those with R′ = 2‐C6H4OMe (5a, d) decomposed in solution at room temperature. In donor solvents, the chelate ring opens giving the stable solvated complexes [CpRe(NO){P(Ph)(R)(R′)}](solvent)]BF4 (solvent = CH3CN, THF) (6b−e, 7d). The new compounds are thus suitable starting materials for the syntheses of diastereomeric rhenium complexes [CpRe(NO){P(Ph)(R)(R′)}(L)]BF4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

show abstract

“…Elemental analysis of the solid and 31 P NMR confirmed that the product was [Ru(l-Cl)Cl(CO) 2 -(detp)] 2 . Although halide-bridged dimers containing small phosphines have been previously reported [38,[50][51][52][53] examples of ruthenium carbonyl halidebridged dimers containing bulky phosphanes are less common [54][55][56].…”

Section: Non-chelated Complexesmentioning
confidence: 99%

Synthesis, characterization, reactivity and theoretical studies of ruthenium carbonyl complexes containing ortho-substituted triphenyl phosphanes
Moreno
¹
,
Haukka
²
,
Jääskeläinen
³

et al. 2005
Journal of Organometallic Chemistry
36
2
15
0
View full text Add to dashboard Cite

Synthesis of new (cyclopentadienyl)rutheniumphosphine complexes with hemilabile ether-phosphines. The X-ray structure of (η5-C5H5)RuCl(Ph2PCH2CH2OCH3)2

Cited by 22 publications

References 17 publications

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (S_Ru,R_C/R_Ru,S_C)- [Ru(η⁵-C₉H₇)(PPh₃){η²(P,O)-Ph₂PCH(Me)C(Bu^t)O}][PF₆] and (S_Ru,R_C/R_Ru,S_C<

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (S_Ru,R_C/R_Ru,S_C)- [Ru(η⁵-C₉H₇)(PPh₃){η²(P,O)-Ph₂PCH(Me)C(Bu^t)O}][PF₆] and (S_Ru,R_C/R_Ru,S_C<

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

Synthesis, characterization, reactivity and theoretical studies of ruthenium carbonyl complexes containing ortho-substituted triphenyl phosphanes

Contact Info

Product

Resources

About

Synthesis of new (cyclopentadienyl)rutheniumphosphine complexes with hemilabile ether-phosphines. The X-ray structure of (η5-C5H5)RuCl(Ph2PCH2CH2OCH3)2

Cited by 22 publications

References 17 publications

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (SRu,RC/RRu,SC)- [Ru(η5-C9H7)(PPh3){η2(P,O)-Ph2PCH(Me)C(But)O}][PF6] and (SRu,RC/RRu,SC<

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (SRu,RC/RRu,SC)- [Ru(η5-C9H7)(PPh3){η2(P,O)-Ph2PCH(Me)C(But)O}][PF6] and (SRu,RC/RRu,SC<

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

Synthesis, characterization, reactivity and theoretical studies of ruthenium carbonyl complexes containing ortho-substituted triphenyl phosphanes

Contact Info

Product

Resources

About

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (S_Ru,R_C/R_Ru,S_C)- [Ru(η⁵-C₉H₇)(PPh₃){η²(P,O)-Ph₂PCH(Me)C(Bu^t)O}][PF₆] and (S_Ru,R_C/R_Ru,S_C<

Intramolecular C−C Bond Formation from β-Keto Phosphine and Allenylidene Ligands in Related Ruthenium(II) Cyclopentadienyl and Indenyl Complexes. X-ray Crystal Structure of (S_Ru,R_C/R_Ru,S_C)- [Ru(η⁵-C₉H₇)(PPh₃){η²(P,O)-Ph₂PCH(Me)C(Bu^t)O}][PF₆] and (S_Ru,R_C/R_Ru,S_C<