European Journal of Inorganic Chemistry p. 1405 - 1414 (2007)
Update date:2022-08-03
Topics:
Brown, Gavin M.
Elsegood, Mark R. J.
Lake, Andrew J.
Sanchez-Ballester, Noelia M.
Smith, Martin B.
Varley, Thomas S.
Blann, Kevin
The new nonsymmetric ditertiary phosphanes, Ph2PCH 2N(R)CH2PAd [3a: R = C6H5, 3b: R = C6H4(4-CH3)] 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 2O)n at 110°C gave the adamantane-derived hydroxymethylphosphane 1, which upon condensation with C6H 5NH2 or C6H4(4-CH 3)NH2 gave the secondary aminophosphanes HN(R)CH 2PAd [2a: R = C6H5, 2b: R = C6H 4(4-CH3)]. Further condensation of 2a or 2b with Ph 2PCH2OH gave 3a or 3b in high yields (ca. 85 %) containing the sterically encumbered adamantane cage. The coordination capabilities of 2a, 3a and 3b have been explored with various PdII, PtII, RuII, IrIII and AuI metal centres. Bridge cleavage of {Pd(κ2-C,N-C16H16N)Br} 2 with 2 equiv. of 2a gave the neutral, mononuclear complex Pd(κ2-C,N-C16H16N)Br(2a) (4). Reaction of 3a/3b with MCl2(cod) (M = Pt, Pd) gave the corresponding κ2-P,P′-chelate complexes cis-MCl2(3) [5a: M = Pt, R = C6H5, 5b: Pt, R = C6H 4(4-CH3), 5c: Pd, R = C6H5, 5d: Pd, R = C6H4(4-CH3)]. In contrast, bridge cleavage of the dimers {RuCl2(η6-p-cym)}2 or {IrCl2(η5-Cp*)}2 with 3a gave the κ1-P-monodentate complexes RuCl2(η6- p-cym)(3a) (6) and IrCl2(η5-Cp*)(3a) (7), respectively, in which the -PAd group is noncoordinating. Reaction of 6 or 7 with AuCl(tht) (tht = tetrahydrothiophene) gave the mixed-metal complexes κ2-P,P′-μ-RuCl2(η6-p-cym) {Ph2PCH2N(Ph)CH2PAd(AuCl)} (8) and κ2-P,P′-μ-IrCl2(η5- Cp*){Ph2PCH2N(Ph)CH2PAd(AuCl)} (9). All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore, the structures of 2a, 4, 5a, 5b and 6-9 have been elucidated by single-crystal X-ray crystallography. The X-ray structures of 5a, 5b and 6-9 represent the first examples of crystallographically characterised nonsymmetric ditertiary phosphane complexes bearing one adamantane moiety. Wiley-VCH Verlag GmbH & Cp. KGaA, 2007.
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