Ruthenium(II)-Komplexe mit dem neuen Liganden (Oxetanyl-2-methyl)diphenylphosphan / Ruthenium(II) Complexes with the Novel Ligand (Oxetanyl-2-methyl)diphenylphosphine

Lindner, Ekkehard; Möckel, A.

doi:10.1515/znb-1992-0514

Cited by 8 publications

References 3 publications

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New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes Containing One Hemilabile Ketophosphane Ligand

Demerseman

2001

Eur. J. Inorg. Chem.

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The reaction of the ketophosphanes Ph2PCH2C(=O)tBu (1), Ph2PCMe2C(=O)iPr (1′), or Ph2PCMe2CH2C(=O)Me (1′′) with a precursor complex RuCl2(L)(η6‐p‐cymene) [L = PMe3 (a), PMePh2 (b), PiPrPh2 (c), PPh3 (d), P(OMe)Ph2 (e), P(OMe)3 (f)] in methanol and under carbon monoxide, provides an access to a novel family of complexes (ttt)‐RuCl2(CO)(L)[η2‐(P,O)‐ketophosphane] (2a−e, 2′a,e,f, and 2′′a) with trans‐chlorine and trans‐phosphorus atoms. Further reaction with carbon monoxide or acetonitrile under thermal activation yields the cis,cis,trans derivatives (cct)‐RuCl2(CO)2(L)[η1‐(P)‐ketophosphane] 4a,b and 4′a, and (cct)‐RuCl2(CO)(MeCN)(L)[η1‐(P)‐ketophosphane] 5a,b,d. Complexes 2a,b and 2′a rearrange under thermal activation, or after exposure to sunlight, into the (ctc and ccc)‐RuCl2(CO)(L)[η2‐(P,O)‐ketophosphane] isomers, with cis‐chlorine and cis‐phosphorus atoms, 6a,b and 6′a, respectively. Complexes 6a,b reversibly add one molecule of carbon monoxide when forming the all‐cis derivatives (ccc)‐RuCl2(CO)2(L)[η1‐(P)‐ketophosphane] 7a,b, respectively. The removal of one chloride ligand in complexes 4a, 4′a, or 5a with silver tetrafluoroborate affords the stable cationic derivatives {RuCl(CO)(L′)(PMe3)[η2‐(P,O)‐ketophosphane]}[BF4], 8a and 8′a (L′ = CO) and 9a (L′ = MeCN), respectively. Mild basic conditions are sufficient to allow the synthesis of the enolatophosphane derivatives (ttt)‐RuCl(CO)2(L)[η2‐(P,O)‐Ph2PCH=C(tBu)O], 10a,c,e, and of the analogous (ccc) and (cct) isomers, 11a,b and 12a, respectively.

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New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes Containing One Hemilabile Ketophosphane Ligand

Demerseman

2001

Eur. J. Inorg. Chem.

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Bis(keto-phosphane) and Bis(enolato-phosphane) Ruthenium Complexes − Synthesis and X-ray Structure Determination of RuCl(NO)[η2-(P,O)-Ph2PCH=C(tBu)O]2

Demerseman

Toupet

2002

Eur. J. Inorg. Chem.

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A slow reaction consisting of a cleavage of one Ru−Cl bond occurred when a mixture of RuCl2[Ph2PCH2C(tBu)=O]2 (1) and [NH4][PF6] was dissolved in methanol as shown by a subsequent reaction with carbon monoxide affording the stable cationic derivative {RuCl(CO)[Ph2PCH2C(tBu)=O]2}[PF6] (2). By contrast, the straightforward reaction of 1 with carbon monoxide yielded RuCl2(CO)[Ph2PCH2C(tBu)=O][Ph2PCH2C(=O)tBu] (3) which contains unreactive Ru−Cl bonds. The isomerization of 2, which is induced under sun light exposure, is the preliminary step to the selective formation of the all‐cis bis(enolato‐phosphane) derivative (ccc)Ru(CO)2[η2‐(P,O)‐Ph2PCH=C(tBu)O]2 (9). The isomeric bis(enolato‐phosphane) derivative (cct)‐Ru(CO)2[η2‐(P,O)‐Ph2PCH=C(tBu)O]2 (10), with trans phosphorus and cis carbonyl ligands, respectively, was selectively obtained under mild basic conditions, starting from (cct)‐RuCl2(CO)2[Ph2PCH2C(=O)tBu]2 (4), which results from the reaction of 3 with carbon monoxide under thermal activation. Through an oxidative addition process, the reaction of 1 with [NO][BF4] yielded {RuCl2(NO)[Ph2PCH2C(tBu)=O][Ph2PCH2C(=O)tBu]}[BF4] (13) with trans phosphorus and trans chloride ligands, respectively. Simple deprotonation of 13 generated the enolato‐phosphane RuIV complex RuCl2(NO)[Ph2PCH=C(tBu)O][Ph2PCH2C(=O)tBu] (14) which retains the same geometry. Under basic conditions, the bis(enolato‐phosphane) derivative RuCl(NO)[η2‐(P,O)‐Ph2PCH=C(tBu)O]2 (15) was obtained. The formation of 15 surprisingly showed a trans to cis rearrangement of the two phosphorus coordinating atoms, as further confirmed by an X‐ray structure determination.

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The Transition Metal Coordination Chemistry of Hemilabile Ligands

Slone

Weinberger

Mirkin

1999

Progress in Inorganic Chemistry

437

255

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Ruthenium(II)-Komplexe mit dem neuen Liganden (Oxetanyl-2-methyl)diphenylphosphan / Ruthenium(II) Complexes with the Novel Ligand (Oxetanyl-2-methyl)diphenylphosphine

Cited by 8 publications

References 3 publications

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes Containing One Hemilabile Ketophosphane Ligand

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes Containing One Hemilabile Ketophosphane Ligand

Bis(keto-phosphane) and Bis(enolato-phosphane) Ruthenium Complexes − Synthesis and X-ray Structure Determination of RuCl(NO)[η2-(P,O)-Ph2PCH=C(tBu)O]2

The Transition Metal Coordination Chemistry of Hemilabile Ligands

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