Phosphaniminatokomplexe von Molybdän / Phosphaneiminato Complexes of Molybdenum

Abstract

<jats:p>We report the syntheses and IR spectra of phosphanciminato complexes of molybdenum:</jats:p><jats:p>(Mo<jats:sup>V</jats:sup>Cl<jats:sub>4</jats:sub>(NPPh<jats:sub>3</jats:sub>)(PPh<jats:sub>3</jats:sub>)] (I)</jats:p><jats:p>PPh<jats:sub>4</jats:sub>[MoIVCl<jats:sub>4</jats:sub>(NPPh<jats:sub>3</jats:sub>)(PPh<jats:sub>3</jats:sub>)] · 2CCl<jats:sub>4</jats:sub> (II)</jats:p><jats:p>PPh<jats:sub>4</jats:sub>[MoVCl<jats:sub>5</jats:sub>(NPCl<jats:sub>3</jats:sub>)] (III)</jats:p><jats:p>I is obtained from [MoNCl<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> and triphenylphosphane, or from [MoCl<jats:sub>4</jats:sub>(NSCl)]<jats:sub>2</jats:sub> and triphenylphosphane: II was prepared by reacting MoNCl<jats:sub>4</jats:sub> with triphenylphosphane followed by treatment with tetraphenylphosphonium chloride; III can be generated from PPh<jats:sub>4</jats:sub>[MoNCl<jats:sub>4</jats:sub>] with PCl<jats:sub>3</jats:sub>/PCl<jats:sub>5</jats:sub>. Complex I is paramagnetic (μeff, = 1.83 B.M., d<jats:sup>1</jats:sup>-configuration): II is diamagnetic (d<jats:sup>2</jats:sup>-system).</jats:p>

Stable Analogs of the Uranyl Ion Containing the −NUN− Group

“…Phosphorane iminato groups might be expected to possess a weaker trans influence than the oxo group, because the M−N bond is considerably longer than the M−O bond. However, the available structural data is sparse, − and all that can be said is that the magnitudes of the trans influences of iminato and oxo groups are similar and substantial …”

Synthese und Kristallstruktur des Phosphaniminatokomplexes [MoCl4(NPPh3)(Pyridin)] · CH2Cl2/ Synthesis and Crystal Structure of the Phosphaneiminato Complex [MoCl4(NPPh3)(pyridine)] · CH2Cl2

“…D ie P h o sp h anim inatokom plexe M oC l4 (N P P h 3) [7] und [M oCl4(N P P h 3 )(P P h 3)] [8 ] lassen sich auch durch U m setzungen nach ((2) bzw. (3)) erh alten : …”