New Inorganic Metallacycles and the First Six-Membered Covalent “True” Heterocycle – Oxidation of RC(E)NHPPh2 (E = O or S; R = H2N, Ph, or Py) with O, S, or Se to Give RC(E)NHP(E′)Ph2 (E′ = O, S, Se) and Their Coordination Chemistry

Abstract

Direct oxidation of PhC(O)NHPPh2, H2NC(S)NHPPh2, (C5H4N)C(S)NHPPh2 with O2, S8, or Se gives [PhC(O)NHP(O)Ph2] (1), [H2NC(S)NHP(S)Ph2] (2), [H2NC(O)NHP‐(S)Ph2] (3), [PhC(O)NHP(S)Ph2] (4), [(C5H4N)C(S)NHP(S)Ph2] (5), and [H2NC(S)NHP(Se)Ph2] (6). Deprotonation of 1, 2, 4–6 with potassium tert‐butoxide gives K[PhC(O)NP(O)Ph2] (7), K[H2NC(S)NP(S)Ph2] (8), K[PhC(O)NP(S)Ph2] (9), K[(C5H4N)C(S)NP(S)Ph2] (10), and K[H2NC(S)NP(Se)Ph2] (11). Reaction of 4with KOBu and [Cu(Ph3P)2][NO3] gives [Cu(Ph3P)(PhC(O)NP(S)Ph2)] (12) which is the first crystallographically characterised example of a non‐ionic six‐membered “true” heterocycle (i.e. a ring in which every heterocatom is different). 9 and 10 were treated with [PdCl2(COD)] to give [Pd{PhC(O)NP(S)Ph2}2] (13) and [Pd{(C5H4N)C(O)NP(S)Ph2}2] (14), respectively The anion of 8 coordinates to zinc forming [Zn{H2NC(S)NP(S)Ph2}2] (15). Treatment of 2 or 8 with [PtCl2(COD)] gives [Pt{H2NC(S)NP(S)Ph2}{H2NC(S)NHP(S)Ph2}]+Cl− (16) and [Pt{H2NC(S)NP(S)Ph2}2] (17), respectively. The X‐ray structures of 12, 15–17are reported.

Coordination Mode of the Zinc(II) and Cadmium(II) Cations with N‐(Diisopropoxyphosphoryl)thiobenzamide

“…The structure of Zn II and Cd II complexes with the general formula M[L‐ S , S′ ] 2 {L = [H 2 NC(S)NP(S)(C 6 H 5 ) 2 ] – , M = Zn II ;16 L = [C 6 H 5 NHC(S)NP(S)(O i Pr) 2 ] – , M = Zn II or Cd II ;17 L = [C 6 H 5 C(S)NP(S)(O i Pr) 2 ] – , M = Zn II[17] and Cd II[18] } has been investigated by IR and NMR spectroscopy16–18 and X‐ray analysis 16. It was established that, in all cases, there is chelate formation in which the metal cation has a distorted tetrahedral MS 4 environment.…”

Ether functionalised aminophosphines: synthesis and co-ordination chemistry of palladium(II) and platinum(II) complexes †

“…For example, rhodium() 3 and platinum() 4 complexes of chiral aminophosphines have proved to be efficient catalysts for asymmetric hydrogenation and hydroformylation reactions respectively, and nickel complexes have been employed 5 in the cyclodimerisation of buta-1,3-diene. In addition, Woollins and co-workers have reported a number of examples of aminophosphines including those derived from 1,2-diaminobenzene 6 and Ph 2 PNHCOPh, 7 and aminophosphines of the type Ph 2 PNHC 6 H 4 COR have also recently been reported. 8 The chemistry of ether phosphines has received considerable † Electronic supplementary information (ESI) available: rotatable 3-D crystal structure diagram in CHIME format.…”

4-Bromo-N-(diisopropoxyphosphoryl)benzamide

“…For related structures, see: Chekhlov (1990); Safin et al (2009); Safin, Sokolov, Nö th et al (2008);Solov'ev et al (1990). For the chemistry of phosphine derivatives of urea and thiourea, see: Birdsall et al (1999). For the use of bidentate organophosphorus ligand systems, see: Crespo et al (2004); Safin et al (2006) and for the transport and extraction of metal ions, see: Luckay et al (2009a,b).…”

“…The chemistry of phosphine derivatives of urea and thiourea was first studied during the 1960 s (Birdsall et al, 1999).…”