A hydrogen atom in an organoplatinum-amine system. 1. Synthesis and spectroscopic and crystallographic characterization of novel zwitterionic complexes with a Pt(II)[sup [minus]][center dot][center dot][center dot]H-N[sup +] unit

Journal Article · Wed Dec 02 04:00:00 EST 1992 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00051a025· OSTI ID:6396264

Wehman-Ooyevaar, I C.M.; Grove, D M; Kooijman, H; Sluis, P van der; Spek, A L; Koten, G van ^[1]

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1. Univ. of Utrecht (Netherlands)

The unusual bridging-hydrogen complexes PtX(L-C,N)(LH-C,H) containing a zwitterionic Pt(II)[sup [minus]][center dot][center dot][center dot]H-N[sup +] moiety have been obtained in a reaction of cis-Pt(L-C,N)[sub 2] with R[sub 2]SnX[sub 2] (R = Me, Ph; X = Cl, Br) in a mixture of CH[sub 2]Cl[sub 2] and MeOH. The chelating amine ligand systems L used in this reaction are [1-C[sub 10]H[sub 6]NMe[sub 2]-8][sup [minus]], [C[sub 6]H[sub 4]CH[sub 2]NMe[sub 2]-2][sup [minus]], and [C[sub 6]H[sub 4]CH[sub 2]NEt[sub 2]-2][sup [minus]]. The complex PtCl(1-C[sub 10]H[sub 6]NMe[sub 2]-8-C,N)(1-C[sub 10]H[sub 6]NHMe[sub 2]-8-C,H) can also be obtained by reaction of cis-Pt(1-C[sub 10]H[sub 6]NMe[sub 2]-8-C,N)[sub 2] with dry HCl. The bridging proton of the zwitterionic Pt(II)[sup [minus]][center dot][center dot][center dot]H-N[sup +] moiety shows a characteristic [sup 1]H NMR resonance at ca. 11-16 ppm with a [sup 1]J([sup 195]Pt,[sup 1]H) of ca. 65-180 Hz; the latter decreases with increasing ligand flexibility. In the Pt[center dot][center dot][center dot]H-N moiety of the PtX(L-C,N)(LH-C,H) complexes, an increase of the Pt[center dot][center dot][center dot]H interaction is associated with a simultaneous decrease of the H-N interaction. When L is chiral [C[sub 6]H[sub 4]CH(Me)NMe[sub 2]-(R)-2][sup [minus]], cis-Pt(L-C,N)[sub 2] affords in a reaction with Me[sub 2]SnBr[sub 2] the nonbridging complex PtBr(C[sub 6]H[sub 4]CH(Me)NMe[sub 2]-(R)-2-C,N)(C[sub 6]H[sub 4]CH(Me)NHMe[sub 2]-(R)-2-C) as the major product. The X-ray crystal structures of both a bridging complex and a nonbridging complex are described. Especially the latter shows good evidence that the bridging interaction is largely electrostatic. Internal steric influences only affect the stability of the bridging moiety when they arise from groups on the benzylic carbon atom. 48 refs., 5 figs., 4 tabs.

• OSTI ID: 6396264
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 114:25; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINES
CHARGED PARTICLES
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
HYDROGEN COMPLEXES
IONS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PLATINUM COMPLEXES
RESONANCE
SCATTERING
STEREOCHEMISTRY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION