Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric Ditertiary Phosphanes Derived from R₂PCH₂OH

Abstract

The new nonsymmetric ditertiary phosphanes, Ph 2 PCH 2 N-(R)CH 2 PAd [3a: R = C 6 H 5 , 3b: R = C 6 H 4 (4-CH 3 )] were prepared using a three-step sequence of condensation reactions. Hence treatment of AdP-H (AdP-H = 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane) with (CH 2 O) n at 110°C gave the adamantane-derived hydroxymethylphosphane 1, which upon condensation with C 6 H 5 NH 2 or C 6 H 4 (4-CH 3 )-NH 2 gave the secondary aminophosphanes HN(R)CH 2 PAd [2a: R = C 6 H 5 , 2b: R = C 6 H 4 (4-CH 3 )]. Further condensation of 2a or 2b with Ph 2 PCH 2 OH gave 3a or 3b in high yields

Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

“…The P···P separation in 10 is 4.487 Å whilst the Ru···Au separation is 7.162 Å. Both are smaller than those previously documented [24] and is a consequence of the longer P-C-N-C-P backbone between the two different phosphorus centres than observed here with 1 (P-C-C-P). The intermolecular Au···Au separation [5.594 Å] infers no significant aurophilic interactions between neighbouring P-Au-Cl units.…”

“…Within the coordination sphere of 5 the Ru-P, Ru-Cl and Ru-C arene bond lengths are comparable to those of the halfsandwich ruthenium(II) complex [RuCl 2 (η 6 -p-cymene){κ 1 -P-Ph 2 PCH 2 N(Ph)CH 2 PAd}] recently described by us. [24] Similarly the Ir-P, Ir-Cl and Ir-C centroid metric parameters are comparable to those of other iridium(III) half-sandwich compounds. [24,36] The P···P separations within 5 and 7·CHCl 3 (1) 112.3 (2) www.eurjic.org Table 4.…”

“…[24] Similarly the Ir-P, Ir-Cl and Ir-C centroid metric parameters are comparable to those of other iridium(III) half-sandwich compounds. [24,36] The P···P separations within 5 and 7·CHCl 3 (1) 112.3 (2) www.eurjic.org Table 4. The Ru II centre (Figure 5) remains coordinated to the -PPh 2 group of 1 and the other coordination sites are occupied by two chlorides and (2) an η 6 -p-cymene arene ligand.…”

“…[15][16][17][18][19][20][21][22][23] We recently reported the synthesis and coordination studies of a new nonsymmetric ditertiary phosphane containing a P-C-N(R)-C-P skeletal backbone in which one of the P-based moieties was a phosphaadamantane cage. [24] The presence of a bulky adamantane cage imposed on this ligand the ability to adopt a range of ligating modes including κ 1 -P-monodentate coordination upon complexation to [RuCl 2 (η 6 -p-cymene)] or [IrCl 2 (η 5 -Cp*)] metal fragments. [24] In an effort to promote other coordinating capabilities employing the unique steric properties of the phosphaadamantane group we report here a simple one-step hydrophosphination procedure by which a new saturated two-carbon spacer ditertiary phosphane bearing non-equivalent groups (-PPh 2 and -PAd) can be prepared.…”

“…[24] The presence of a bulky adamantane cage imposed on this ligand the ability to adopt a range of ligating modes including κ 1 -P-monodentate coordination upon complexation to [RuCl 2 (η 6 -p-cymene)] or [IrCl 2 (η 5 -Cp*)] metal fragments. [24] In an effort to promote other coordinating capabilities employing the unique steric properties of the phosphaadamantane group we report here a simple one-step hydrophosphination procedure by which a new saturated two-carbon spacer ditertiary phosphane bearing non-equivalent groups (-PPh 2 and -PAd) can be prepared. Pringle and co-workers [25] recently reported the synthesis of nonsymmetric diphosphanes based on a rigid ethene backbone and furthermore, upon coordination, the disposition of the phosphorus groups gave exclusive κ 2 -che-lation to square-planar metal centres.…”