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Abstract

The 1+1 reaction of the symmetrical dimers [ClP(m-N t Bu)] 2 1 and [H 2 NP(m-N t Bu)] 2 2 in thf-Et 3 N gives the tetrameric macrocycle [{P(m-N t Bu)} 2 NH] 4 3 (67%); consisting of four P 2 (m-N t Bu) 2 rings linked by endo N-H groups.

Selection of a Pentameric Host in the Host–Guest Complexes {[{[P(μ‐NtBu)]2(μ‐NH)}5]⋅I}−[Li(thf)4]+ and [{[P(μ‐NtBu)]2(μ‐NH)}5]⋅HBr⋅THF

“…An analogous situation has been demonstrated in the selection of a cyclic porphyrin tetramer (as opposed to the cyclic porphyrin dimer) from a linear porphyrin dimer, using a tetradentate template. [12] The fact that 1 is generated almost exclusively at À78 AE 25 8C in the absence of LiI in THF (in the 1:1 stoichiometric reaction), [3] but that 2 is generated almost exclusively in the presence of LiI at reflux in THF (in the 2:3 stoichiometric reaction) provides qualitative support for the view that the major effect of I À is as a negative template, that is, resulting in a drastic reduction in the rate of I 4 ! 1 rather than an increase in I 4 !…”

“…[13] [{NH 2 P(m-NtBu)} 2 ] was prepared by the reaction of [{ClP(m-NtBu)} 2 ] with a saturated NH 3 /THF solution. [3,4] The compounds 2·HBr·THF and 2·I{Li(thf) 4 } were isolated and characterised with the aid of an N 2 -filled glove box fitted with a Belle Technology O 2 and H 2 O internal recirculation system. Melting points were determined by using a conventional apparatus and sealing samples in capillaries under N 2 .…”

“…[3] A minor product of this reaction (0.5-1 % yield) is the host-guest complex [{[P(m-NtBu)] 2 (m-NH)} 5 ]·HCl·THF (2·HCl·THF), in which the Cl À ion is coordinated nearly symmetrically within the cavity of the macrocyclic pentamer [{[P(m-NtBu) 2 ] 2 (m-NH)} 5 ] (2) by five NÀH···Cl hydrogen bonds (Figure 1b). [4] Since the hydrogen atom of the HCl unit in 2·HCl·THF could not be located in the X-ray crystallographic study, and spectroscopic studies proved inconclusive, there remains some uncertainty as to the exact composition of this species, for example, whether the HCl unit is intact or whether the H + ion is bonded to the N or P atoms of 2.…”

“…[1] However, the prospect that this cyclic dimer might represent a broader range of homologous macrocycles of this type [2] was not realised until recently. [3,4] By reducing the steric demands of the linking groups we were able to obtain the cyclic tetramer …”

Mono‐, Bi‐, Tri‐ and Tetranuclear Palladium(II), Copper(I), and Gold(I) Complexes of Morpholine‐ and N‐Methylpiperazine‐Functionalized Cyclodiphosph(III)azans, cis‐[(tBuN‐μ)2(PNC4H8X)2] (X = O, NMe)

“…CuI was purchased from Aldrich and used without further purification. The precursors [ClP(µ-NtBu)] 2 , [11] [PdCl 2 (SMe 2 ) 2 ], [12] [Pd(µ-Cl)(η 3 -C 3 H 5 )] 2 , [13] and [AuCl(SMe 2 )] [14] were prepared according to the published procedures. mass spectrometry experiments were carried out with a Waters QTof micro-YA-105 instrument.…”