LATE TRANSITION METAL COMPLEXES WITH HYPERVALENT ORGANOPHOSPHORUS(III) LIGANDS

A
a Covaci,

D.

a Marginean,

A.

b Laguna,

M. Conception

b* Gimeno,

and A. Silvestru

a*

Babes-Bolyai University, Faculty of Chemistry & Chemical Engineering, RO-400028 Cluj-Napoca, Romania, E-mail : ancas@chem.ubbcluj.ro bDepartamento de Quimica Inorganica, Instituto de Ciencia de Materiales de Aragon, Universidad de ZaragozaCSIC, E50009, Zaragoza, Spain, E-mail : gimeno@unizar.es

Introduction
Transition metal complexes containing neutral phosphines as ligands were extensively investigated in last years due to their properties and potential applications in catalysis, optical devices, special materials or as biologically active compounds. Our interests are focused on the synthesis, structural characterization, properties and reactivity of some transition metal complexes with neutral organophosphorus(III) ligands of type PhP(C6H4CH2NMe2-2)2.

Solution NMR studies

Au(1)

Synthesis

8.0 ppm (f1)

7.0

6.0

5.0

4.0

3.0

2.0

7.0 ppm (t1)

6.0

5.0

4.0

3.0

The new gold derivatives [AuCl{PPh(C6H4CH2NMe2-2)2}] (1) and [Au(C6F5){PPh(C6H4CH2NMe2-2)2}] (2) were prepared by reacting PhP(C6H4CH2NMe2-2)2 with [AuX(tht)] (X = Cl, C6F5). The thioato complex (3) was obtained by reacting [AuCl{PPh(C6H4CH2NMe2-2)2}] with C6F5SH in presence of K2CO3 (Scheme1). The complexes [CdCl2{PPh(C6H4CH2NMe2-2)2}] (3), [ZnCl2{PPh(C6H4CH2NMe2-2)2}] (4), [PdCl2{PPh(C6H4CH2NMe2-2)2}] (5), [CuCl2{PPh(C6H4CH2NMe2-2)2}] (6), were obtained by reacting PhP(C6H4CH2NMe2-2)2 with the corresponding metal dichloride, MCl2 (M = Cd, Zn, Pd, Cu) in a 1:1 molar ratio (Scheme 2). The solution behavior of compounds 1 - 5 was investigated by 1H, 31P and 13C NMR spectroscopy. The solid-state molecular structures of 1, 2 and 3 were established by single-crystal X-ray diffraction.
NMe2 Ph P Au Cl AuCltht PPh
2

1H

NMR Spectrum of [AuCl{PPh(C6H4CH2NMe2-2)2}] (a) and [ZnCl2{PPh(C6H4CH2NMe2-2)2}] (b)

Single crystal X-ray diffraction studies

[AuCl{PPh(C6H4CH2NMe2-2)2}]
N(2)

Selected bond lengths [] and angles [deg]

C(21) P(1) C(11)

NMe2 Ph P Au SC6F5

Cl(1)

Au(1)

C(1)

N(1)

Au(1)-P(1) Au(1)-Cl(1) N(1)-P(1) N(1)Au(1)nonbonding P(1)-Au(1)-Cl(1)

2.240(17) 2.294(16) 3.082(15) 3.45082) 175.49(2)

NMe2

C6F5SH

NMe2
2

Au(1)

AuR(tht) R= C6F5

Ph P Au R

Scheme 1
NMe2 Ph P MCl2

NMe2 PPh + MCl2

M = Cd, Zn, Pd, Cu

Scheme 2
Compound PhP(C6H4CH2NMe2-2) 2 [AuCl{PPh(C6H4CH2NMe2-2)2}] [Au(C6F5){PPh(C6H4CH2NMe2-2)2}] [Au(SC6F5){PPh(C6H4CH2NMe2-2)2}] [CdCl2{PPh(C6H4CH2NMe2-2)2}] [ZnCl2{PPh(C6H4CH2NMe2-2)2}] [PdCl2{PPh(C6H4CH2NMe2-2)2}] [CuCl2{PPh(C6H4CH2NMe2-2)2}] M.p. oC % 54 132 123 154.7 211.9 178.8 163.9 82 37 33 92 60 49.66 38.33 40.2 Colour yellow 31P, ppm -15.1

colorless 18.21 colorless 30.8 colorless colorless colorless yellow yellow 23.9 -22.7 -22.9 16.0
paramagnetic

Polymer association in the crystal of compound 1 based on ClH contacts. H(27b)Cl(1) Cl(1)H(29b) H(14Cl(1) vdw(Cl,H) ca. 2.853(17) 2.967(20) 2.780(31) 3.01 [1] Au1)P(1) 2.240(17) cov(Au,P) ca. 1.92 [1] vdw(Au,P) ca. 3.60 [1]

Conclusions Acknowledgements
Financial support from the Ministery of Education and Research of ROMANIA (Project CNCSIS 12/1456/2007) is highly acknowledged. All complexes were isolated as crystalline solids. Their NMR (1H, 13C, 31P) spectra areconsistent with complexation. Single crystal X-ray diffraction studies revealed a linear coordination geometry around the gold atom. In case of compound 1 supramolecular networks are formed by short ClH contacts.