Metallacumulenes: Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=CR1R2]+ and trans-[(Ph2PCH2PPh2)2Ru(=C=C=C(OMe)CH=CPh2)2]2+ Derivatives

Loic Toupet; Mohammed Fettouhi; Lahcene Ouahab; Daniel Touchard; Nadine Pirio; Pierre H. Dixneuf

doi:10.1021/om00011a050

Metallacumulenes: Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph₂PCH₂PPh₂)₂(Cl)Ru=C=C=CR¹R²]⁺ and trans-[(Ph₂PCH₂PPh₂)₂Ru(=C=C=C(OMe)CH=CPh₂)₂]²⁺ Derivatives

Loic Toupet
, Mohammed Fettouhi
, Lahcene Ouahab
, Daniel Touchard^*
, Nadine Pirio
, Pierre H. Dixneuf

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

65 Scopus citations

Abstract

cis-RuCl₂(Ph₂PCH₂PPh₂)₂(1) reacts with pentadiynes XC≡CC≡CCPh₂(OSiMe₃) [2 (X = H) and 3 (X = Bu₃Sn)], but in the presence of NaPF₆, to afford trans-(Ph₂PCH₂PPh₂)₂(Cl)-RuC≡CC≡CCPh₂(OSiMe₃) (4). On protonation with HBF₄ complex 4 in methanol leads to allenylidene trans-[(Ph₂PCH₂PPh₂)₂(Cl)Ru=C=C=C(OMe)CH-CPh₂]X (5a) (a: X = BF₄) and in dichloromethane to trans-[(Ph₂PCH₂PPh₂)₂(Cl)Ru=C=C=CCH=C(Ph)(o-C₆H₄)]X (6a) via electrophilic ortho-substitution within the metallacumulene intermediate LnRu=C=C=C=C= CPh₂]X (A). Alternatively, complex 1 and diyne 2 with NaPF₆afford in one step allenylidenes 5b (b: X = PF₆) in methanol and 6b in dichloromethane. Bis(diynyl) derivative trans-(Ph₂-PCH₂PPh₂)₂Ru[(C=CC=CC(OSiMe₃)Ph₂])₂ (7), obtained by reaction of 2 with 1 and HNⁱPr₂, on protonation with HBF₄ in methanol offered a direct route to the first bis(allenylidene) complex trans-[(Ph₂PCH₂PPh₂)₂Ru(=C=C=C(OMe)CH=CPh₂)₂](BF₄)₂(8). The X-ray diffraction studies of two allenylidene complexes 6b and 8 are reported. The structure of 6b consists of two different allenylidene cations. That of 8 shows coplanar allenylidene ligands with a strong contribution of a ynyl resonance structure.

Original language	English
Pages (from-to)	5263-5272
Number of pages	10
Journal	Organometallics
Volume	14
Issue number	11
DOIs	https://doi.org/10.1021/om00011a050
State	Published - Nov 1995
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Dive into the research topics of 'Metallacumulenes: Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph₂PCH₂PPh₂)₂(Cl)Ru=C=C=CR¹R²]⁺ and trans-[(Ph₂PCH₂PPh₂)₂Ru(=C=C=C(OMe)CH=CPh₂)₂]²⁺ Derivatives'. Together they form a unique fingerprint.

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Toupet, L., Fettouhi, M., Ouahab, L., Touchard, D., Pirio, N., & Dixneuf, P. H. (1995). Metallacumulenes: Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph₂PCH₂PPh₂)₂(Cl)Ru=C=C=CR¹R²]⁺ and trans-[(Ph₂PCH₂PPh₂)₂Ru(=C=C=C(OMe)CH=CPh₂)₂]²⁺ Derivatives. Organometallics, 14(11), 5263-5272. https://doi.org/10.1021/om00011a050

@article{21a288a84b724a958d692c0b4b6a94c2,

title = "Metallacumulenes: Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=CR1R2]+ and trans-[(Ph2PCH2PPh2)2Ru(=C=C=C(OMe)CH=CPh2)2]2+ Derivatives",

abstract = "cis-RuCl2(Ph2PCH2PPh2)2(1) reacts with pentadiynes XC≡CC≡CCPh2(OSiMe3) [2 (X = H) and 3 (X = Bu3Sn)], but in the presence of NaPF6, to afford trans-(Ph2PCH2PPh2)2(Cl)-RuC≡CC≡CCPh2(OSiMe3) (4). On protonation with HBF4 complex 4 in methanol leads to allenylidene trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=C(OMe)CH-CPh2]X (5a) (a: X = BF4) and in dichloromethane to trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=CCH=C(Ph)(o-C6H4)]X (6a) via electrophilic ortho-substitution within the metallacumulene intermediate LnRu=C=C=C=C= CPh2]X (A). Alternatively, complex 1 and diyne 2 with NaPF6afford in one step allenylidenes 5b (b: X = PF6) in methanol and 6b in dichloromethane. Bis(diynyl) derivative trans-(Ph2-PCH2PPh2)2Ru[(C=CC=CC(OSiMe3)Ph2])2 (7), obtained by reaction of 2 with 1 and HNiPr2, on protonation with HBF4 in methanol offered a direct route to the first bis(allenylidene) complex trans-[(Ph2PCH2PPh2)2Ru(=C=C=C(OMe)CH=CPh2)2](BF4)2(8). The X-ray diffraction studies of two allenylidene complexes 6b and 8 are reported. The structure of 6b consists of two different allenylidene cations. That of 8 shows coplanar allenylidene ligands with a strong contribution of a ynyl resonance structure.",

author = "Loic Toupet and Mohammed Fettouhi and Lahcene Ouahab and Daniel Touchard and Nadine Pirio and Dixneuf, \{Pierre H.\}",

year = "1995",

month = nov,

doi = "10.1021/om00011a050",

language = "English",

volume = "14",

pages = "5263--5272",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "11",

}

Toupet, L, Fettouhi, M, Ouahab, L, Touchard, D, Pirio, N & Dixneuf, PH 1995, 'Metallacumulenes: Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph₂PCH₂PPh₂)₂(Cl)Ru=C=C=CR¹R²]⁺ and trans-[(Ph₂PCH₂PPh₂)₂Ru(=C=C=C(OMe)CH=CPh₂)₂]²⁺ Derivatives', Organometallics, vol. 14, no. 11, pp. 5263-5272. https://doi.org/10.1021/om00011a050

Metallacumulenes: Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph₂PCH₂PPh₂)₂(Cl)Ru=C=C=CR¹R²]⁺ and trans-[(Ph₂PCH₂PPh₂)₂Ru(=C=C=C(OMe)CH=CPh₂)₂]²⁺ Derivatives. / Toupet, Loic; Fettouhi, Mohammed; Ouahab, Lahcene et al.
In: Organometallics, Vol. 14, No. 11, 11.1995, p. 5263-5272.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Metallacumulenes

T2 - Activation of Diynes and Formation of New Allenylideneruthenium Complexes. Crystal Structures of trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=CR1R2]+ and trans-[(Ph2PCH2PPh2)2Ru(=C=C=C(OMe)CH=CPh2)2]2+ Derivatives

AU - Toupet, Loic

AU - Fettouhi, Mohammed

AU - Ouahab, Lahcene

AU - Touchard, Daniel

AU - Pirio, Nadine

AU - Dixneuf, Pierre H.

PY - 1995/11

Y1 - 1995/11

N2 - cis-RuCl2(Ph2PCH2PPh2)2(1) reacts with pentadiynes XC≡CC≡CCPh2(OSiMe3) [2 (X = H) and 3 (X = Bu3Sn)], but in the presence of NaPF6, to afford trans-(Ph2PCH2PPh2)2(Cl)-RuC≡CC≡CCPh2(OSiMe3) (4). On protonation with HBF4 complex 4 in methanol leads to allenylidene trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=C(OMe)CH-CPh2]X (5a) (a: X = BF4) and in dichloromethane to trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=CCH=C(Ph)(o-C6H4)]X (6a) via electrophilic ortho-substitution within the metallacumulene intermediate LnRu=C=C=C=C= CPh2]X (A). Alternatively, complex 1 and diyne 2 with NaPF6afford in one step allenylidenes 5b (b: X = PF6) in methanol and 6b in dichloromethane. Bis(diynyl) derivative trans-(Ph2-PCH2PPh2)2Ru[(C=CC=CC(OSiMe3)Ph2])2 (7), obtained by reaction of 2 with 1 and HNiPr2, on protonation with HBF4 in methanol offered a direct route to the first bis(allenylidene) complex trans-[(Ph2PCH2PPh2)2Ru(=C=C=C(OMe)CH=CPh2)2](BF4)2(8). The X-ray diffraction studies of two allenylidene complexes 6b and 8 are reported. The structure of 6b consists of two different allenylidene cations. That of 8 shows coplanar allenylidene ligands with a strong contribution of a ynyl resonance structure.

AB - cis-RuCl2(Ph2PCH2PPh2)2(1) reacts with pentadiynes XC≡CC≡CCPh2(OSiMe3) [2 (X = H) and 3 (X = Bu3Sn)], but in the presence of NaPF6, to afford trans-(Ph2PCH2PPh2)2(Cl)-RuC≡CC≡CCPh2(OSiMe3) (4). On protonation with HBF4 complex 4 in methanol leads to allenylidene trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=C(OMe)CH-CPh2]X (5a) (a: X = BF4) and in dichloromethane to trans-[(Ph2PCH2PPh2)2(Cl)Ru=C=C=CCH=C(Ph)(o-C6H4)]X (6a) via electrophilic ortho-substitution within the metallacumulene intermediate LnRu=C=C=C=C= CPh2]X (A). Alternatively, complex 1 and diyne 2 with NaPF6afford in one step allenylidenes 5b (b: X = PF6) in methanol and 6b in dichloromethane. Bis(diynyl) derivative trans-(Ph2-PCH2PPh2)2Ru[(C=CC=CC(OSiMe3)Ph2])2 (7), obtained by reaction of 2 with 1 and HNiPr2, on protonation with HBF4 in methanol offered a direct route to the first bis(allenylidene) complex trans-[(Ph2PCH2PPh2)2Ru(=C=C=C(OMe)CH=CPh2)2](BF4)2(8). The X-ray diffraction studies of two allenylidene complexes 6b and 8 are reported. The structure of 6b consists of two different allenylidene cations. That of 8 shows coplanar allenylidene ligands with a strong contribution of a ynyl resonance structure.

UR - https://www.scopus.com/pages/publications/0000931273

U2 - 10.1021/om00011a050

DO - 10.1021/om00011a050

M3 - Article

AN - SCOPUS:0000931273

SN - 0276-7333

VL - 14

SP - 5263

EP - 5272

JO - Organometallics

JF - Organometallics

IS - 11

ER -