Metathetical Exchange between Metal–Metal Triple Bonds

Abstract

The reaction of the molybdenum−molybdenum triple-bonded dimer (CO) 2 CpMoMoCp(CO) 2 (Cp = η 5 -C 5 H 5 ) with the triple-bonded dimetallynes Ar iPr4 MMAr iPr4 or Ar iPr6 MMAr iPr6 (Ar3 ) 2 ; M = Ge, Sn, or Pb) under mild conditions (≤80 °C, 1 bar) afforded Ar iPr4 MMoCp(CO) 2 or Ar iPr6 MMoCp(CO) 2 in moderate to excellent yields. The reactions represent the first isolable products from a metathesis of two metal−metal triple bonds. Analogous exchange reactions with the single-bonded (CO) 3 CpMo−MoCp(CO) 3 gave ArM ̈−MoCp(CO) 3 (Ar = Ar iPr4 or Ar iPr6 ; M = Sn or Pb). The products were characterized by NMR ( 1 H, 13 C, 119 Sn, or 207 Pb), electronic, and IR spectroscopy and by X-ray crystallography.

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

“…This type of terphenyl‐rhodium coordination is already known in the literature [21] . Both heteroelement NMR signals were found at high frequencies ( 119 Sn NMR 8 , 3112 ppm; 207 Pb NMR 9 , 11 269 ppm) in comparison to known organometallostannylenes or plumbylenes [7, 17, 18, 22] . Cationic complex [Cp*W(CO) 3 Sn(NHC)][Al(OC(CF 3 ) 3 ) 4 ] exhibits a 119 Sn NMR signal at very high frequency (3318 ppm) [17b] …”

“…The Group 14 elements show signals in the 119 Sn and 207 Pb NMR spectra at 1149 ppm ( 10 : ddt, 1 J 119Sn‐103Rh =762 Hz, 2 J 119Sn‐31P =294 Hz, 2 J 119Sn‐31P =185 Hz) and 5729 ppm ( 11 : d, 1 J 207Pb‐103Rh =1050 Hz). The chemical shifts of the tetrylidynes lie in the range of complexes featuring triple bonds with molybdenum Mo≡E (Sn: 1021 ppm, Pb 9660 ppm) or niobium Nb≡Sn 829.7 ppm [3c, 7] . In the 13 C{ 1 H} NMR spectra the signals for the ipso carbon atom connected at tin or lead exhibit the signal at highest frequency (Sn: 188.0 ppm, Pb 274.7 ppm).…”

“…Most recently Power et al. presented with the metathetical exchange between metal‐metal triple bonds of transition metal molybdenum and main group metals Ge, Sn and Pb a very elegant synthetic method for the synthesis of carbyne homologues (Cp(CO) 2 Mo≡E‐Ar*, E=Ge, Sn, Pb) [7] . Known homologues of transition metal carbyne complexes and new entries reported in this contribution are summarized in Figure 1 [8] …”

Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

“…Die Gruppe‐14‐Elemente weisen ihre Signale im 119 Sn‐ und 207 Pb‐NMR‐Spektrum bei 1149 ppm ( 10 : ddt, 1 J 119Sn‐103Rh =762 Hz, 2 J 119Sn‐31P =294 Hz, 2 J 119Sn‐31P =185 Hz) und 5729 ppm ( 11 : d, 1 J 207Pb‐103Rh =1050 Hz) auf. Diese chemischen Verschiebungen der Tetrylidine liegen im Bereich der Molybdänkomplexe Mo≡E (Sn: 1021 ppm, Pb 9660 ppm) sowie einer Niobverbindung Nb≡Sn 829.7 ppm [3c, 7] . Im 13 C{ 1 H}‐NMR entsprechen die Signale der zinn‐ bzw.…”

“…Jüngst präsentierten Power et al. mit dem metathetischen Austausch zwischen Metall‐Metall‐Dreifachbindungen des Übergangsmetalls Molybdän und den Hauptgruppenmetallen Ge, Sn und Pb eine sehr elegante Methode zur Synthese der Carbinhomologen (Cp(CO) 2 Mo≡E‐Ar*, E=Ge, Sn, Pb) [7] . In Abbildung 1 ist eine Übersicht bekannter Homologe der Übergangsmetallcarbin‐Komplexe und die neuen Beiträge dieser Arbeit dargestellt [8] …”