trans-Tetrachlorobis[(E)-ethyl 2-(1-iminopropoxyimino)propanoate]platinum(IV)

Abstract

Key indicatorsSingle-crystal X-ray study T = 100 K Mean (C-C) = 0.004 Å R factor = 0.020 wR factor = 0.042 Data-to-parameter ratio = 19.0 For details of how these key indicators were automatically derived from the article, see

Kinetic and Thermodynamic Aspects of the Regioselective Addition of Bifunctional Hydroxylaminooxime-type HO-Nucleophiles to Pt-Complexed Nitriles

“…Among the latter, attention should be drawn to the coupling between metal-complexed nitriles and bifunctional nucleophiles bearing the same (e.g., diphosphines, dioximes, , and diamines) and different (amino alcohols, salicylaldoximes, mixed sulfimide/sulfides, hydroxy/phosphines, and oxime/hydrazones) nucleophilic sites. 1,2-Hydroxylaminooximes ( 1 and 2 ) are bifunctional HO-nucleophiles insofar as both N and O atoms from the hydroxylamine NHOH moiety and O atom from the oxime CNOH group exhibit nucleophilic properties; − their reactions with and the regioselectivity of their addition to complexed nitriles have not been studied to date.…”

“…The FAB + -MS spectra of 5-8 display molecular ion peaks and/or a characteristic fragmentation for [PtCl n (imine) 2 ] compounds, corresponding to the loss of Cl's from the molecular ion, viz., [M -nCl] + ; these data agree well with those observed for the previously characterized platinum imino complexes. [13][14][15][17][18][19][20][21][22] In the IR spectra, 5-8 give no bands from ν(CtN) stretching vibrations in the range between 2400 and 2270 cm -1 {such bands appear at 2340 cm -1 (vs) for trans-[PtCl 4 (EtCN) 2 ] 34 and 2314 cm -1 (m) for trans-[PtCl 2 (EtCN) 2 ] 35 } but show one (for 5, 7, 8) or two (for 6) intense bands in the range of 1660-1595 cm -1 assigned to ν(CdN) of the newly formed imino group Cd NH and the free oxime group CdNOH from the HNd CEtON(H)CMe 2 C(R)dNOH ligand; these data match well with those for similar complexes derived from the addition of "simple" oximes, e.g., [PtCl n {NHdC(Me)ONdCR 1 -R 2 2 } 2 ], 15,17,18,20 or dialkyl-and dibenzylhydroxylamines, e.g., [PtCl n {NHdC(Et)ONR 3 2 } 2 ], 14 to Pt-bound nitriles. The addition of the 1,2-hydroxylaminooximes 1 and 2 to the nitrile platinum(II) and -(IV) complexes trans-[PtCl 2 -(EtCN) 2 ] and trans-[PtCl 4 (EtCN) 2 ], respectively, was monitored by 1 H, 13 C, 15 N, and 195 Pt NMR spectroscopy, and selected data are presented in Table 1.…”

“…Following our ongoing project investigating various reactivity modes of complexed organonitriles (i.e., nucleophilic [1][2] and electrophilic [1][2][3]11 additions and [2 + 3] dipolar cycloadditions 12 ), we extended our previous works on the metalmediated hydroxylamine-nitrile 13,14 and oxime-nitrile [15][16][17][18][19][20][21][22] couplings to such combined bifunctional HO-nucleophiles, i.e., 1,2-hydroxylaminooximes (see boxed compounds in-Figure 1; IUPAC names 2-hydroxyamino-2-methyl-1-phenylpropan-1-one oxime, 1, and 3-hydroxyamino-3-methylbutan-2-one oxime, 2), where the N atoms of the HON functional groups are in sp 3 and sp 2 hybridization, respectively. The distinct hybridization should determine different nucleophilic properties of the HO moieties of the hydroxylaminooxime species.…”

trans-Bis[(E)-acetoneO-propanimidoyloxime-κN′]tetrachloroplatinum(IV)

“…Previously, we have reported the crystal structures of trans-[PtCl 4 {NH C(R)ON CR 0 R 00 2 } 2 ] [R = R 0 = R 00 = Me (Kukushkin et al, 2000); R = Me, R 0 = Cl, R 00 = C 6 H 4 -4-NO 2 (Garnovskii et al, 2000); R = Me, R 0 = Cl, R 00 = p-Tol (Garnovskii et al, 2000); R = R 0 = Me, R 00 = C(Me) NOH (Kukushkin et al, 2000); R = Et, R 0 = Ph, R 00 = OH (Luzyanin et al, 2002); R = Et, R 0 = H, R 00 = Mes (Bokach et al, 2003); R = Et, R 0 = H, R 00 = COPh (Makarycheva-Mikhailova et al, 2003); R = Et, R 0 = MeO, R 00 = Mes (Luzyanin et al, 2004); R = Et, R 0 = Me, R 00 = C(Ph) NNH 2 (Garnovskii et al, 2004); R = Et, R 0 = Me, R 00 = C(Ph) NN CH(C 6 H 3 -2-OH-5-NO 2 ) (Garnovskii et al, 2004); R = Et, R 0 = Me, R 00 = COOEt (Luzyanin et al, 2005); R = Me, R 0 = R 00 = C 5 H 10 (Kukushkin et al, 1998)]. Here, we report the X-ray structure of one more representative of this class of compounds, the title complex trans- The coordination polyhedron of the centrosymmetric complex (I) (Fig.…”