Phosphido-bridged mixed-metal (ruthenium/cobalt) compounds via the reaction of (arene)RuCl2(PPh2X) (X = H, Cl) with Co2(CO)8: x-ray structure of RuCo2(.mu.-PPh2)2(.mu.-CO)(CO)7

Regragui, Rachid; Dixneuf, Pierre H.; Taylor, Nicholas J.; Carty, Arthur J.

doi:10.1021/om00085a010

Cited by 35 publications

(14 citation statements)

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“…Monosubstitution by P(OMe), takes place preferentially at Co (2). Substitution at Co (1) was not observed, perhaps because of the steric inhibition resulting from the proximity of four phosphido-phenyl groups to this metal atom, although electronic factors may also play an important role.…”

Section: (B) Reaction Ofmentioning

confidence: 97%

Synthesis of [Co₂(µ-PPh₂C₃H₄)(µ-PPh₂)(CO)₄]; its reactions with P(OMe)₃and with alkynes

Caffyn¹,

Mays²,

Solan³

et al. 1993

J. Chem. Soc., Dalton Trans.

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The bis(phosphid0) -bridged complex [Co,(p-PPh,),(CO),] 1 undergoes an insertion reaction of allene into one of the phosphido bridges, to give the new ligand-bridged dinuclear cobalt complex [Co,(p-PPh,C,H,)(p-PPh,) (CO),] 2 in high yield. Complex 2 reacts with P(OMe), to give the monosubstituted derivative [Co,(p-PPh,C,H,) (p-PPh,) (CO),{P(OMe),}] 3 in which substitution has occurred at the allyl-co-ordinated cobalt atom. Complex 2 also reacts with alkynes, RCECH (R=CH,OH, Me or H), which insert into the remaining phosphido bridge along with a molecule of CO to give [Co,(p-PPh,C,H,){p-PPh,C(O)CHCR}(CO),] (R = CH,OH 4a. Me 4b or H 4c). In the case of MeCSCH which gives 4b. a second isomer, [CO,(~-PP~,C,H,){~-PP~,C(O)CM~CH}(CO)~] 5, which differs in the mode of insertion of the alkyne, is also obtained. The isomeric complexes [Co,(p-PPh,C(O)CHCR}(p-PPh,)(CO),] ( R = CH,OH 6a or Me 6b) and [CO,(~-PP~,C(O)CRCH}(~-PP~,)(CO),] (R = CH,OH 7a or M e 7b), which may be regarded respectively as analogues of 4 and 5 but with a phosphido bridge and an additional terminal CO group in place of the p-PPh,C,H, ligand, have been prepared from [Co,(p-RCCH)(CO),] (R = CH,OH or Me) and P,Ph,. The complexes [Co,(p-PPh,CHCRC(O)}(p-PPh,)(CO),](R = CH,OH 8a or M e 8b). which are also isomers of complexes 6a. 7a and 6b. 7b respectively, have also been obtained in these latter reactions. The complexes 8 contain a bridging ligand which differs from that present in 6 and 7 in that t h e ordering of the PPh,, alkene and CO components of the bridging ligand is not the same. The crystal structures of the complexes 3 and 4c have been determined by X-ray diffraction studies.The insertion of alkynes into the metal-phosphorus bonds of phosphido-bridged dinuclear complexes is more common than originally thought and usually gives new dinuclear complexes with a bridging ligand derived from one phosphido group, one molecule of alkyne and sometimes also a CO or -C=CR group if these are present in the original complex. '-*Starting from the bis(phosphid0)-bridged complex [Co,-(p-PPh,),(CO),] 1, we recently reported the stepwise synthesis of the complexes [Co,{ p-PPh,CR'=CR2C(0)CR3=CR4-PPh2}(C0),] (R = H, alkyl, aryl, C0,Me or silyl).' These complexes each contain a bridging nine-membered dimetallacyclic ring formed from the coupling of both phosphido groups in 1 with two alkyne molecules and one CO molecule. In the light of this ability of [Co,(p~-PPh~)~(C0)~1 1 to undergo alkyne insertions to give novel ligand-bridged species we decided to explore its reactivity with allene.In this paper we present a study of the reaction of 1 with allene and of the reactivity of the product, [Co,(p-PPh,C,H,)-(p-PPh,)(CO),] 2, towards P(OMe), and alkynes (Scheme 1). The reactions of 2 with alkynes, R C S H , gives the alkyneinserted products [Co2(p-PPh2C3H,){p-PPh2C(0)CHCR)-(CO),] (R = CH,OH 4a, Me 4b or H 4c) and [Co,(p-PPh,-C,H,){ p-PPh,C(O)CRCH)(CO),] (R = Me 5). For comparative purposes the five-membered metallacyclic ring-containing complexes [Co, { p-PPh,C(O)CHCR}...

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Section: (B) Reaction Ofmentioning

confidence: 97%

Synthesis of [Co₂(µ-PPh₂C₃H₄)(µ-PPh₂)(CO)₄]; its reactions with P(OMe)₃and with alkynes

Caffyn¹,

Mays²,

Solan³

et al. 1993

J. Chem. Soc., Dalton Trans.

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“…For instance, the reaction of [Ru 3 (CO) 12 ] with PPh 2 H affords [Ru 2 (u-PPh 2 ) 2 (CO) 6 ] (103) (M = Ru, X = PPh 2 , L = CO) as one of the products 211. ' 212 The same product is also obtained by photolysis of [Ru 3 (CO)9 (PPh 2 H) 3 ],213 by thermolysis of [Ru 3 (u-PPh 2 ) 2 (ja-H) 2 (CO) 8 ]214 and from the reaction of [RuCl 2 (p-cymene)(PPh 2 X)] (X = H or Cl) with [Co 2 (CO)8 ] 215. Similarly, reaction of [Ru 3 (CO) 12 ] with AsMe 2 H produces [Ru 2 (u-AsMe 2 )(CO) 6 ] (103) (M = Ru, X = AsMe 2 , L = CO) 216.…”

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confidence: 82%

Binuclear Complexes of Ruthenium and Osmium Containing Metal Metal Bonds

Haines¹

1995

Comprehensive Organometallic Chemistry II

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“…It was also obtained as a side-product in many reactions involving Ru 3 (CO) 12 and diphenylphosphine [78][79][80][81][82][83][84].…”

Section: Phosphato Phosphinato Phosphinito and Phosphido Derivativesmentioning

confidence: 99%

Sawhorse-type diruthenium tetracarbonyl complexes

Therrien

Süß‐Fink

2009

Coordination Chemistry Reviews

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Phosphido-bridged mixed-metal (ruthenium/cobalt) compounds via the reaction of (arene)RuCl2(PPh2X) (X = H, Cl) with Co2(CO)8: x-ray structure of RuCo2(.mu.-PPh2)2(.mu.-CO)(CO)7

Cited by 35 publications

References 3 publications

Synthesis of [Co₂(µ-PPh₂C₃H₄)(µ-PPh₂)(CO)₄]; its reactions with P(OMe)₃and with alkynes

Synthesis of [Co₂(µ-PPh₂C₃H₄)(µ-PPh₂)(CO)₄]; its reactions with P(OMe)₃and with alkynes

Binuclear Complexes of Ruthenium and Osmium Containing Metal Metal Bonds

Sawhorse-type diruthenium tetracarbonyl complexes

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Phosphido-bridged mixed-metal (ruthenium/cobalt) compounds via the reaction of (arene)RuCl2(PPh2X) (X = H, Cl) with Co2(CO)8: x-ray structure of RuCo2(.mu.-PPh2)2(.mu.-CO)(CO)7

Cited by 35 publications

References 3 publications

Synthesis of [Co2(µ-PPh2C3H4)(µ-PPh2)(CO)4]; its reactions with P(OMe)3and with alkynes

Synthesis of [Co2(µ-PPh2C3H4)(µ-PPh2)(CO)4]; its reactions with P(OMe)3and with alkynes

Binuclear Complexes of Ruthenium and Osmium Containing Metal Metal Bonds

Sawhorse-type diruthenium tetracarbonyl complexes

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Product

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Synthesis of [Co₂(µ-PPh₂C₃H₄)(µ-PPh₂)(CO)₄]; its reactions with P(OMe)₃and with alkynes

Synthesis of [Co₂(µ-PPh₂C₃H₄)(µ-PPh₂)(CO)₄]; its reactions with P(OMe)₃and with alkynes