Reactivity of Deprotonated Mn2(.mu.-H)(.mu.-PCyH)(CO)8: Selective Monoauration to Mn2(.mu.-AuPR3)(.mu.-PCyH)(CO)8 and Mn2(.mu.-H)(.mu.3-PCy(AuPR3))(CO)8 (R = Cy, Ph, p-C6H4F, p-C6H4OMe) and Kinetic Studies of their Conversion

Haupt, H.‐J.; Schwefer, M.; Egold, Hans; Floerke, U.

doi:10.1021/ic00126a015

Cited by 28 publications

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“…Interestingly, the reverse reaction (P-H reductive elimination) seems to be thermodynamically favoured at anionic derivatives containing bent phosphinidene bridges, as observed for the cluster [Os 3 (l-H)(l 2 -PPh)(CO) 10 ] − , 8 and proposed for the dimanganese anion [Mn 2 (l-H)(l-PCy)(CO) 8 ] − (Scheme 2). 9 Taking into account the above considerations and given our current interest in the chemistry of both phosphinidene-bridged complexes, 10,11 and unsaturated binuclear cations, 12 we decided to study in more detail the protonation reaction leading to the above mentioned phosphinidene cation. In order to analyze the influence of the organic substituent on phosphorus, we have also studied the protonation reactions of the hydride-phosphide complexes [Mo 2 Cp 2 (l-H)(l-PHR)(CO) 4 ] having mesityl (1b), Scheme 2 Reported type of processes relating bridging phosphide and phosphinidene ligands (terminal ligands on metal atoms omitted for clarity, see text).…”

Section: Introductionmentioning

confidence: 99%

Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo₂Cp₂(µ-H)(µ-PHR)(CO)₄] (R = Cy, 2,4,6-C₆H₂R′₃; R′ = H, Me,^tBu)

et al. 2004

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The new hydride complexes [Mo2Cp2(mu-H)(mu-PHR)(CO)4] having bulky substituents (R = 2,4,6-C(6)H2tBu3= Mes*, R = 2,4,6-C6H2Me3= Mes) have been prepared in good yield by addition of Li[PHR] to the triply bonded [Mo2Cp2(CO)4] and further protonation of the resulting anionic phosphide complex [Mo2Cp2(mu-PHR)(CO)4]-. Protonation of the Mes* compound with either [H(OEt2)2][B{3,5-C6H3(CF3)2}4] or HBF4.OEt2 gives the cationic phosphinidene complex [Mo2Cp2(mu-H)(mu-PMes*)(CO)4]+ in high yield. In contrast, protonation of the analogous hydride compounds with Mes or Cy substituents on phosphorus give the corresponding unsaturated tetracarbonyls [Mo2Cp2(mu-PHR)(CO)4]+, which are unstable at room temperature and display a cis geometry. Decomposition of the latter give the electron-precise pentacarbonyls [Mo2Cp2(mu-PHR)(mu-CO)(CO)4]+, also displaying a cis arrangement of the metal fragments. In the presence of BF4- as external anion, fluoride abstraction competes with carbonylation to yield the neutral fluorophosphide hydrides [Mo2Cp2(mu-H)(mu-PFR)(CO)4]. Similar results were obtained in the protonation reactions of the hydride compounds having a Ph substituent on phosphorus. In that case, using HCl as protonation reagent gave the chloro-complex [Mo2ClCp2(mu-PHPh)(CO)4] in good yield. The structures and dynamic behaviour of the new compounds are analyzed on the basis of solution IR and 1H, 31P, 19F and 13C NMR data as well as the X-ray studies carried out on [Mo2Cp2(mu-H)(mu-PHMes)(CO)4](cis isomer), [Mo2Cp2(mu-H)(mu-PFMes)(CO)4](trans isomer), [Mo2Cp2(mu-PHCy)(mu-CO)(CO)4](BF4) and [Mo2ClCp2(mu-PHPh)(CO)4].

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Section: Introductionmentioning

confidence: 99%

Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo₂Cp₂(µ-H)(µ-PHR)(CO)₄] (R = Cy, 2,4,6-C₆H₂R′₃; R′ = H, Me,^tBu)

et al. 2004

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“…Another topic of our preparative efforts was combined with the determination of the reactivity pattern of the complex type M 2 (m-H)(m-PCyH)(CO) 8 (M = Mn, Re) to ascertain selective monoauration and diauration products. The results obtained are described in our earlier papers [6][7][8] . To compare chemical properties of the homologue transition metals, the cluster Mn 2 (AuPR 3 ) 2 (m 4 -PCy)(CO) 8 which shows a topomerization process which was triggered by the m 4 -P bridging atom was prepared.…”

Section: Preparationmentioning

confidence: 75%

Modern aspects on tri- and tetranuclear cluster complexes supported by phosphido bridges

Haupt

2000

J Chem Sci

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This report on small cluster complexes with metal-metal bonds in the field of coordination chemistry documents results in the following scientific areas. (1) Systematic synthetic routes via ditransition metal carbonyl derivative of manganese and rhenium (group 7) to functionalized triangulo-and tetrahedro-clusters including structural characterization, (2) Dynamic properties of mono-and diauration isomers like M 2 (m-AuPR 3)(m-PCyH)(CO) 8 /M 2 (m-H)(m 3-PCy(AuPR 3))(CO) 8 (isomerization) and M 2 (m-AuPR 3) 2 (m 4-PCy)(CO) 8 /M 2 (m-AuPR 3)(m 3-PCy(AuPR 3))(CO) 8 (M = Mn, Re; R = organic residue) (rearrangement and valence isomerization) and MM¢ (m-H)(m-PCy 2)(m 4-PCy(AuPR 3))(CO) 6 (M = M¢ , M ¹ M¢) (topomerization) going from one to the other homologue and the kinetic study of isomerization in the framework Re 2 (AuPCy 3) 2 (m-PMeN 2 (m-C(Bu)O)(CO) 6 , (3) Correlations of chirality transfer in diastereomeric tetrahedro-clusters Re 2 (M 1 PR 3) 2 (m-PCy 2)(CO) 7 (h 1-L*) (M 1 = coin metals, L* = chiral ligand as (+) or (-) prolinate, for example) from CD data. These selected contributions will be discussed to answer the question "Do small cluster complexes remain as a future challenge in cluster chemistry?"

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“…The counting of one further VE from the AuPPh 3 fragment and 8e – from the four CO groups yields 34e – for the dimanganese fragment, which supports the existence of a Mn–Mn single bond according to the 18 VE rule. A related dimanganese complex, [Mn 2 (CO) 8 (μ-PCyH)(μ-AuPPh 3 )], with a bridging (μ-PHR) phosphido ligand and (μ-AuPPh 3 ) unit reveals very similar structural and spectroscopic properties. The Mn–Mn bond length in 4 (3.076 Å) lies within the normal range of known Mn–Mn distances (2.664–3.244 Å for complexes with a (CO) 4 Mn–Mn(CO) 4 fragment and 3.040–3.136 Å for compounds of the type Mn 2 (CO) 8 (μ-AuPR 3 )(μ-PR 2 ) according to the Cambridge Structural Database).…”

Section: Resultsmentioning

confidence: 99%

Transformation of a Phosphorus-Bound Cp* Moiety in the Coordination Sphere of Manganese Carbonyl Complexes

et al. 2013

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The reaction of Cp*PCl 2 with K[Mn(CO) 5 ] yields two novel anionic products, [Mn 2 (CO) 8 (μ-PC 11 H 14 O)] − (1 − ) and [Mn 2 (CO) 8 (μ-PHCp*)] − (2 − ), instead of the expected phosphinidene complexes with a delocalized Mn−P−Mn bond system. By treating these anionic complexes with [Ph 3 PAuCl], they are converted into corresponding neutral derivatives [Mn 2 (CO) 8 (μ-PC 11 H 14 O)(μ-AuPPh 3 )] (3) and [Mn 2 (CO) 8 (μ-PHCp*)(μ-AuPPh 3 )] (4). NMR investigations and X-ray structural analyses for 1 − , 3, and 4 show that the compounds 1 − and 3 as well as 2 − and 4 reveal similar molecular structures in which the neutral complexes 3 and 4 contain AuPPh 3 units bridging Mn−Mn bonds. In comparison to 1 and 3, complexes 2 and 4 possess one additional H atom bound at the P atom. The structures of 1 and 3 include a novel bicyclic unit consisting of a C 5 ring of the former Cp* moiety conjugated to a CCC(O)P four-membered ring. The latter is built by a CO group of a former Mn carbonyl fragment connecting a P and a C atom of the cycle. One of the methyl groups of the Cp* ligand became a CH 2 unit, resulting in two isomers containing an exocyclic CH 2 moiety in the positions three or five of the C 5 ring. Both isomers were found in the reaction mixture, with one as the major isomer. The proposed reaction pathway is based on XRD, NMR, and MS data and includes the reduction of a transient [Cp*P(Mn(CO) 5 ) 2 ] complex by [Mn(CO) 5 ] − , a proton transfer from the neutral to the reduced complex, and a successive reduction of the protonated species. The neutral bicyclic compound 3, containing a 2phosphacyclobutanone ring, is light sensitive and decomposes to tetramethylfulvene, possibly by a radical decarbonylation mechanism via a transient phosphacyclobutane derivative, [C 5 (CH 3 ) 4 (CH 2 )P(Mn(CO) 4 ) 2 AuPPh 3 ] (5), detected by NMR spectroscopy.

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Reactivity of Deprotonated Mn2(.mu.-H)(.mu.-PCyH)(CO)8: Selective Monoauration to Mn2(.mu.-AuPR3)(.mu.-PCyH)(CO)8 and Mn2(.mu.-H)(.mu.3-PCy(AuPR3))(CO)8 (R = Cy, Ph, p-C6H4F, p-C6H4OMe) and Kinetic Studies of their Conversion

Cited by 28 publications

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Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo₂Cp₂(µ-H)(µ-PHR)(CO)₄] (R = Cy, 2,4,6-C₆H₂R′₃; R′ = H, Me,^tBu)

Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo₂Cp₂(µ-H)(µ-PHR)(CO)₄] (R = Cy, 2,4,6-C₆H₂R′₃; R′ = H, Me,^tBu)

Modern aspects on tri- and tetranuclear cluster complexes supported by phosphido bridges

Transformation of a Phosphorus-Bound Cp* Moiety in the Coordination Sphere of Manganese Carbonyl Complexes

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Reactivity of Deprotonated Mn2(.mu.-H)(.mu.-PCyH)(CO)8: Selective Monoauration to Mn2(.mu.-AuPR3)(.mu.-PCyH)(CO)8 and Mn2(.mu.-H)(.mu.3-PCy(AuPR3))(CO)8 (R = Cy, Ph, p-C6H4F, p-C6H4OMe) and Kinetic Studies of their Conversion

Cited by 28 publications

References 0 publications

Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo2Cp2(µ-H)(µ-PHR)(CO)4] (R = Cy, 2,4,6-C6H2R′3; R′ = H, Me,tBu)

Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo2Cp2(µ-H)(µ-PHR)(CO)4] (R = Cy, 2,4,6-C6H2R′3; R′ = H, Me,tBu)

Modern aspects on tri- and tetranuclear cluster complexes supported by phosphido bridges

Transformation of a Phosphorus-Bound Cp* Moiety in the Coordination Sphere of Manganese Carbonyl Complexes

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Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo₂Cp₂(µ-H)(µ-PHR)(CO)₄] (R = Cy, 2,4,6-C₆H₂R′₃; R′ = H, Me,^tBu)

Proton induced P–H and Mo–H bond activation at the phosphide bridged dimolybdenum complexes [Mo₂Cp₂(µ-H)(µ-PHR)(CO)₄] (R = Cy, 2,4,6-C₆H₂R′₃; R′ = H, Me,^tBu)