The 1992 Alcan Award Lecture Excursions around the periodic table: ligand design in inorganic chemistry

Abstract

An overview is given on the strategy used to come up with the design of a new type of ligand that is appropriate for coordination to both the late metals and the early metals. The coordination chemistry of the potentially tridentate ligand −N(SiMe2CH2PR2)2 is developed starting with the Ni triad and then the heavier members of group 9, namely rhodium and iridium. It is with iridium that reactive fragments such as methylene and vinylidene have been stabilized and their chemistry examined. Extension to groups 3, 4, and the lanthanides is also discussed. With these elements, phosphine coordination imparts new reactivity patterns such as alkane elimination with group 3 and dinitrogen activation with group 4. In addition, the side-on binding mode for N2 attached to a dinuclear zirconium system is also presented.

Highlights in the Renaissance of Amidometal Chemistry

“…The synthesis of lanthanoid amidophosphane complexes is possible with the amidophosphane hybrid ligands developed by Fryzuk et al [11,12] Biligand complexes are accessible, depending upon the lanthanoid ion, by reaction of the lithiated ligand precursor or potassium salt with LnCl 3 .…”

“…[60] Comprehensive NMR investigations and X-ray crystallographic analysis suggested no agostic interactions with the extremely electron-deficient scandium ion. These can be regarded formally as 12 Compounds with diamidodiphosphane ligands possess totally different frontier orbitals.…”

“…polymerizes ethylene. The X-ray structure analysis of 24 shows an anion ± cation separation of 2.487 (12 4 ] leads to a cationic zirconium complex which polymerizes 1-hexene as well as ethylene. A linear relationship between the catalyst/1-hexene ratio and the mean molecular weight (M w /M n`1 /1) confirms the ªlivingº character of the 1-hexene polymerization.…”

1993 ALCAN Award Lecture Chemical binding within and between inorganic rings; the design and synthesis of molecular conductors

“…The present article continues a "traditionn initiated in 1992 by the Canadian Journal of Chemistry to provide a forum for the recipient of the annual ALCAN Award to summarize the highlights of the award lecture in a short monograph (1). Like my oral presentation at Sherbrooke, this account will focus more on recent events, but it is instructive (to me at least) to begin with a personal account of the historical origins of our research.…”

Boryl‐Pinzettensysteme: neue Wege in der Borchemie

“…Einige der charakteristischen Eigenschaften der Liganden sind: starre dreizähnige Bindungstaschen, die mit vielen Übergangsmetallen kompatibel sind, gute Steuerungsmöglichkeiten an einer Reihe von Schlüssel-positionen, exakte Einstellung der inneren und/oder äußeren Koordinationssphäre des Metallions und die Integration zahlreicher Elemente an der koordinierenden Brückenkopf-position. Neben den prototypischen Kohlenstoffgerüsten [12,13] gibt es mittlerweile auch Gerüste mit Heteroatomdonoren in Form von Amido-, [14] Silyl- [15] oder Phosphidoeinheiten. [16] In den letzten Jahren sind auch verschiedene neutrale Pinzettenliganden intensiv untersucht worden, einschließlich Systeme, bei denen eine reversible Ladungsumschaltung von neutral zu monoanionisch stattfindet.…”