Exo-metal coordination by a tricyclic [{P(µ-N-2-NC₅H₄)}₂(µ-O)]₂dimer in [{P(µ-N-2-NC₅H₄)}₂(µ-O)]₂{CuCl·(C₅H₅N)₂}₄{2-NC₅H₄= 2-pyridyl, C₅H₅N = pyridine)

Abstract

The in situ reaction of the phosphazane dimer [CIP(mu-N-2-NC5H4)]2 (2) with CuCl in the presence of CsH5N/H2O gives the title complex [(P(mu-N-2-NC5H4))2(mu-O)]2(CuCl x (C5H5N)2)4 (1), containing a tricyclic [(P(mu-N-2-NC5H4))2(mu-O)]2 ligand which is isoelectronic with species of the type [(P(mu-NR))2NR]2.

The Selenium‐Based Hexameric Macrocycle [(Se)P(μ‐NtBu)2P(μ‐Se)]6

“…[1,2] The tetrameric, nitrogen-bridged macrocycle [{P(m-NtBu)} 2 (m-NH)] 4 (Scheme 1 a) is obtained by the condensation of the dimers [ClP(m-NtBu)] 2 and [(NH 2 )P-(m-NtBu)] 2 in the presence of Et 3 N. [3] However, the pentameric homologue is produced exclusively if this reaction is undertaken in the presence of I À ions, resulting in the hostguest complex [{P(m-NtBu)} 2 (m-NH)] 5 I À (Scheme 1 b). [4] The toroidal structures of the tetramer and pentamer and the presence of endo NÀH functionalities combine the appearance and host-guest characteristics of organic macrocycles such as calixarenes and porphyrins.…”

“…Indeed, the only representative of this type reported to date is the oxygenbridged dimer [{P(m-N(2-py)} 2 (m-O)] 2 (2-py = 2-pyridyl), obtained by hydrolysis of [ClP{m-N(2-py)}] 2 in the presence of CuCl and pyridine. [5] However, we reported a key synthetic step in the potential extension of this methodology to a broader range of macrocycles by showing that oligomerization can be effected between P 2 N 2 units by the reaction of a deprotonated P(H) = O group with a P À Cl bond (Scheme 2). [6] This reaction can be rationalized by a change from a Pcentered to an O-centered nucleophile.…”

A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation

“…1,2 They find applications in various fields such as coordination chemistry, [3][4][5][6][7][8] in anti-tumour studies 9,10 and in catalytic organic transformations. [11][12][13] The dichlorocyclodiphosphazanes, cis-{ClP(μ-NR)} 2 , have been effectively explored as building blocks in the synthesis of a large range of phosphorus-nitrogen macrocycles.…”

The first complex of the pentameric phosphazane macrocycle [{P(μ-NtBu)}2(μ-NH)]5 with a neutral molecular guest: Synthesis and structure of [{P(μ-NtBu)}2(μ-NH)]5(CH2Cl2)2

“…Much of our most recent work in this area has focused on the synthesis and applications of macrocyclic phosph(III)azanes of the type [{P(l-NR)} 2 (l-X)] n (X = NH, O) ( Fig. 1) [4,5]. In contrast to other inorganic macrocycles, the possession of a variety of donor and acceptor functionalities within these species provides the potential for multifaceted coordination behaviour.…”

“…In contrast to other inorganic macrocycles, the possession of a variety of donor and acceptor functionalities within these species provides the potential for multifaceted coordination behaviour. The Cu(I) complex [{P(l-NR)} 2 (l-O)] 2 (CuCl AE 2-pyridine) 4 [5] (R = 2-pyridyl) and the host-guest adduct {[{P(l-N t Bu)} 2 (l-NH)] 5 the two types of coordination behaviour identified so far, i.e. : (i) exo coordination of metals by P centres at the periphery of the rings and (ii) the coordination of anions within the macrocyclic cavities.…”