Reactivity of {Ru(C5Me5)[η2-P,O-Ph2PCH2C(tBu)=O](CO)}[PF6] towards Terminal Alkynes and Unexpected Rearrangement of a Fischer-Type Carbene Ligand

被引：1

作者：

Demerseman, Bernard ^{[1
]}

Toupet, Loic ^{[1
]}

机构：

[1] Univ Rennes 1, CNRS, UMR 6226, F-35042 Rennes, France

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2009年 / 28期

关键词：

Carbene ligands; Cyclopentadienyl ligands; Metallacycles; Phosphane ligands; Ruthenium; VINYLIDENE COMPLEXES; CRYSTAL-STRUCTURE; SUBSTITUTION; RUTHENIUM; DERIVATIVES; CHEMISTRY; CENTERS; OLEFINS; TOOL;

D O I：

10.1002/ejic.200900574

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The ruthenium complex {Ru(C5Me5)[eta(2)-P,O-Ph2PCH2C-(tBu)=O](CO)}[PF6] reacts with terminal alkynes HC CR (R = H, tBu, Ph) in methanol to afford {Ru[:C(OMe)-CH2R](C5Me5)[eta(1)-P-Ph2PCH2C(=O)tBu](CO)}[PF6] derivatives. The similar reaction conducted in dichloromethane as solvent led to six-membered metallacyclic complexes {Ru(C5Me5)[eta(2)-C,P-:C(CH2R)OC(tBu)=CH-PPh2](CO)}[PF6], which, when R is an aromatic group (R = Ph, p-tolyl), rearrange under moderate thermal activation into {Ru(C5Me5)[eta(2)-C,C,P-RCH=CH-OC(tBu)=CHPPh2](CO)}[PF6] derivatives, according to an isomerization of a Fischer-type carbene ligand into an eta(2)-coordinated vinylic ether, as shown by Xray single crystal analysis (R = p-tolyl). ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

引用

页码：4308 / 4313

页数：6

共 40 条

[1] Enolate-phosphane Ligands providing a tool for the selective substitution of triphenylphosphane by carbon monoxide or trimethylphosphane in complex {Ru(Cp)[η2-P,O-Ph2PCH2C(tBu)=O](PPh3)}[PF6], and subsequent reactivity towards terminal Alkynes
Demerseman, B
Toupet, L
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2006, (08) : 1573 - 1581
[2] Synthesis and reactivity of [Ru(Cp*)(L)(MeCN)2][PF6] (L = Ph2POMe or Ph2P-o-tolyl) and {Ru(Cp*)[Ph2PCH2C(tBu)=O](MeCN)}[PF6] complexes, their involvement as catalyst precursors for regioselective allylic substitution reactions and related [Ru(Cp*)Cl(Ph2POMe)(RCHCHCH2)][PF6] η3-allyl ruthenium(IV) intermediates
Demerseman, B
Renaud, JL
Toupet, L
Hubert, C
Bruneau, C
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2006, (07) : 1371 - 1380
[3] Synthesis, structure, and reactivity of functionalized stibanido complexes of iron and ruthenium [(η5-C5Me5)(CO)2MSbR1R2] (M = Fe, Ru; R1, R2 = SiMe3, C(O)tBu, C(O)Ph, C(O)-1 ad)
Weber, L
Mast, CA
Scheffer, MH
Schumann, H
Uthmann, S
Boese, R
Bläser, D
Stammler, HG
Stammler, A
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2000, 626 (02): : 421 - 429
[4] Reactivity of the inversely polarised arsaalkenes R-As=C(NMe2)2 {R = [(η5-C5Me5)(CO)2Fe], tBuC(O)} towards vinylidene complexes [η5-(C5H5)(CO)-(NO)W=C=C(H)R] (R = Ph, tBu)
Weber, Lothar
Bayer, Philipp
Noveski, Gabriel
Stammler, Hans-Georg
Neumann, Beate
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2006, (11) : 2299 - 2305
[5] Synthesis and X-ray crystal structures of the cyclic oxacarbene complexes [Ru{CCH2(CH2)(n)CH2O}(Ph(2)PCH(2)CH(2)PPh(2))(eta-C5H5)][PF6] (n=1 or 2): Boat conformation of the 2-oxacyclohexylidene ligand
Beddoes, RL
Grime, RW
Hussain, ZI
Whiteley, MW
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 526 (02) : 371 - 378
[6] Ligand exchange photochemistry of M2(CO)4(μ-η5,η5-C5H4CH2C5H4) (M = Fe or Ru) and thermal acetylene exchange of Ru2(CO)(μ-CO)[μ-η1:η1-(C6H5)2C2](μ-η5,η5-C5H4CH2C5H4) -: The molecular structures of Ru2(CO)(σ-C6H5)(μ-CO)[μ-P(C6H5)2](μ-η5,η5-C5H4CH2C5H4) and Ru2(CO)(μ-CO)[μ-η1,η3-C6H5C=C(C6H5)O]-(μ-η5,η5-C5H4CH2C5H4)
Bitterwolf, TE
Haener, JL
Shade, JE
Rheingold, AL
Yap, GPA
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 547 (01) : 23 - 33
[7] Reactivity of unsaturated [HOs3(CO)8{μ3-Ph2PCH2PPh(C6H4)}] towards activated alkynes RC∧CR (R=CO2Et, CO2Me)
Haque, Mohd. Rezaul
Alam, Md. Mahbub
Hossain, Md. Kamal
Ghosh, Shishir
Tocher, Derek A.
Mobin, Shaikh M.
Kabir, Shariff E.
INORGANICA CHIMICA ACTA, 2021, 515
[8] Reaction of the pincer-type ligand {2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2)- with [Ph3C]+[PF6]-.: Unprecedented rearrangement and carbon-carbon bond formation
Henn, M
Jurkschat, K
Ludwig, R
Mehring, M
Peveling, K
Schürmann, M
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2002, 628 (13): : 2940 - 2947
[9] Modified synthesis of mixed-ligand dinuclear Ru-Ir, Ru-Rh, and Ru-Ru polyhydride-bridged complexes, CpsRuH3ML (Cps = C5Me5 (Cp*), C5tBu3H2 (Cp‡); M = Rh, Ir, Ru; L = C5(CH3)5, C6H6, p-CH3C6H4CH(CH3)2)
Shimogawa, Ryuichi
Takao, Toshiro
Suzuki, Hiroharu
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2016, 818 : 168 - 178
[10] Synthesis, structure and reactivities of the dinuclear μ-η1:η6-arylethynyl ruthenium complexes [Cp(PR3)2Ru(μ-η1:η6-C≡CC6H4Me-p)RuCp*]•Cl (R = Ph, Me; Cp = η5-C5H5, Cp* = η5-C5Me5).: The molecular structure of [Cp(PPh3)2Ru(μ-η1:η6-C≡CC6H4Me-p)RuCp*]•PF6
Matsuzaka, H
Okimura, H
Sato, Y
Ishii, T
Yamashita, M
Kondo, M
Kitagawa, S
Shiro, M
Yamasaki, M
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2001, 625 (02) : 133 - 139

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