Transition-metal methylene complexes. 14. Reactions of an electron-rich dimetallacyclopropane with protic acids: synthesis and x-ray crystal structures of novel rhodium-methyl and -methylidyne complexes

Herrmann, Wolfgang A.; Plank, Johann; Riedel, Doris; Ziegler, Manfred L.; Weidenhammer, K.; Guggolz, Ernst; Balbach, Barbara

doi:10.1021/ja00391a014

Cited by 70 publications

(17 citation statements)

References 6 publications

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“…This suggests weakening of the P–Rh bond that is offset by strengthening of the Rh–Rh bond, attributed to the interaction with the bridging carbene ligand 49. The latter could also be viewed as a distorted dirhodacyclopropane 50. Analysis of the 103 Rh NMR data reveals that Rh1 is significantly shifted upfield when comparing 7 with 9 and 10 ( δ 103 Rh = –6852, –7184, and –7163 ppm for 7 , 9 and 10 , respectively) further supporting a more electron rich Rh core.…”

Section: Resultsmentioning

confidence: 99%

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

et al. 2019

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Section: Resultsmentioning

confidence: 99%

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

et al. 2019

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“…83.6(4) 150.9(9) 144.7 (9) 87.7(3) 115.9(2) 104.7(3) 103.4(3) 111( 1) 107( 1) 107( 1) 109( 1) 105 (1) the last cycle of refinement are given in Table 1. Interatomic distances and bond angles are listed in Table 2 while selected least-squares planes and interplanar angles are given in Table 3.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and crystal and molecular structure of [(η-C₅H₅)Rh(µ-CO)₂Rh(PPh₃)(η-C₅H₅)] an asymmetric bimetallic complex with a polar rhodium–rhodium bond

Faraone¹,

Brunò²,

Schiavo³

et al. 1983

J. Chem. Soc., Dalton Trans.

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Treatment of [{ Rh(q-C,H,) (CO)),(p-CO)] with PPh3, in saturated hydrocarbons, affords [ (q-C5H5) R h ( ~-c o ) ~R h ( P P h ~) (q-C5H5)] which has been characterized by Lr., 1H n.m.r., and X-ray diffraction methods. The complex crystallizes in the triclinic space group P1, with a = 9.700(2), b = 11.076(2), c = 13.790(3) p\, a = 105.3(1), p = 109.6(1), y = 99.1(1)", and 2 = 2. On the basis of 2 697 reflections with I 2 2.5 o(/), the structure has been refined to R 0.053 and R' 0.059. The molecule possesses a near mirror plane defined by the Rh-Rh bond [2.673(1) A] and the phosphorus atom. The two carbonyl ligands form two different asymmetric bridges to the rhodium atoms [Rh(l)-C(19) 2.17(1), Rh(2)-C(19) 1.89(1), Rh(1)-C(20) 2.10(1), and Rh(2)-C(20) 1.90(1) A].The cyclopentadienyl ligands are in a cis position with an interplanar angle of 66.3" and both are perpendicular to the pseudo-mirror molecular plane. The co-ordination geometry about the two metal centres is different, being formally Rh(1) seven-co-ordinate and Rh(2) six-co-ordinate. The complex [(q-C,H,)Rh(p-CO),Rh(PPh,)(q-C,H,)] reacts with PPh3 to give the known [Rh(q-C5H5)(CO)(PPh3)J ; the same product can be obtained directly by reacting [{Rh(q-C,H,)(CO)),(p-CO)] with PPh3 in excess, in benzene solution.

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“…Bezuglich der allgemeinen Arbeitstechnik sei auf fruhere Experimentalarbeiten 17,30) sowie die Vorbemerkungen zu den Praparatevorschriften von Lit. 3') verwiesen.…”

Section: Experimenteller Teilunclassified

Übergangsmetall‐Methylen‐Komplexe, XXVIII. Carben‐Addition an Metall–Metall‐Mehrfachbindungen. Synthese und Molekülstrukturen neuer μ‐Methylen‐Rhodium‐Komplexe

et al. 1982

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In praktisch quantitativen Ausbeuten reagieren die aliphatischen Diazoverbindungen 2a -o im Temperaturbereich -801 + 25 "C mit dem zweikernigen Carbonylrhodium-Komplex 1 unter Nz-Eliminierung und gleichzeitiger Carben-Addition an die Rh = Rh-,,Doppelbindung" . Der Einflun der Methylen-Brucken auf die Konstitution der neuen Dimetallacyclopropane 3k,l,n,o, 4aj, m und 51 bleibt weitgehend auf sterische Effekte beschrankt und spiegelt sich in den Molekulstrukturen der Schlusselbeispiele 30 und 4g wider. Die teils reversiblen Decarbonylierungs-Reaktionen 3 -, 5 und 4 4 5 verlaufen nach kinetischen Untersuchungen als Direktprozesse ohne Beteiligung von Zwischenstufen signifikanter Konzentration. Das in den Verbindungen 5 wiederhergestellte charakteristische Strukturelement der reaktiven Vorstufe 1 erdffnet mit der konsekutiven Carben-Addition die Moglichkeit zur gezielten Synthese von Bis( p-methylen)-Komplexen mit unterschiedlichen CRz-Liganden (2. B. 6).Reaction of the aliphatic diazo compounds 2ao with the dinuclear carbonylrhodium complex 1 in the temperature range -801 + 25 "C leads to N,-elimination and quantitative carbene addition to the rhodium-rhodium "double bond". The influence of the methylene bridges upon the constitution of the novel dimetallacyclopropane-type compounds 3k,l,n,o, 4 aj,m, and 51 is largely restricted to steric effects which is reflected by the molecular structures of the typical examples 30 and 4g. The decarbonylation reactions 3 + 5 and 4 -+ 5 are in part reversible and, according to kinetic studies, do not involve any intermediate of significant concentration. The structural characteristics of the reactive precursor 1 is reestablished in compounds 5. Consecutive carbene addition to 5 opens a synthetic route to bis(p-methylene) complexes having structurally different CR2-ligands, e. g. 6.

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Transition-metal methylene complexes. 14. Reactions of an electron-rich dimetallacyclopropane with protic acids: synthesis and x-ray crystal structures of novel rhodium-methyl and -methylidyne complexes

Cited by 70 publications

References 6 publications

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

Synthesis and crystal and molecular structure of [(η-C₅H₅)Rh(µ-CO)₂Rh(PPh₃)(η-C₅H₅)] an asymmetric bimetallic complex with a polar rhodium–rhodium bond

Übergangsmetall‐Methylen‐Komplexe, XXVIII. Carben‐Addition an Metall–Metall‐Mehrfachbindungen. Synthese und Molekülstrukturen neuer μ‐Methylen‐Rhodium‐Komplexe

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Transition-metal methylene complexes. 14. Reactions of an electron-rich dimetallacyclopropane with protic acids: synthesis and x-ray crystal structures of novel rhodium-methyl and -methylidyne complexes

Cited by 70 publications

References 6 publications

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

Synthesis and crystal and molecular structure of [(η-C5H5)Rh(µ-CO)2Rh(PPh3)(η-C5H5)] an asymmetric bimetallic complex with a polar rhodium–rhodium bond

Übergangsmetall‐Methylen‐Komplexe, XXVIII. Carben‐Addition an Metall–Metall‐Mehrfachbindungen. Synthese und Molekülstrukturen neuer μ‐Methylen‐Rhodium‐Komplexe

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Synthesis and crystal and molecular structure of [(η-C₅H₅)Rh(µ-CO)₂Rh(PPh₃)(η-C₅H₅)] an asymmetric bimetallic complex with a polar rhodium–rhodium bond