Preparation of trihydridostannyl complexes of rhenium stabilised by isocyanide ligands

doi:10.1016/j.ica.2009.01.029

Inorganica Chimica Acta

Volume 363, Issue 3, 15 February 2010, Pages 605-616

Dedicated to Prof. Paul Pregosin.

https://doi.org/10.1016/j.ica.2009.01.029 Get rights and content

Abstract

Mixed-ligand complexes [ReBr(CO)₂(CNR)_nL₃₋_n] (1–4) [R = 4-CH₃OC₆H₄, 4-CH₃C₆H₄, C(CH₃)₃; L = P(OEt)₃, PPh(OEt)₂; n = 1, 2] were prepared by allowing carbonyl compounds [ReBr(CO)₄L] and [ReBr(CO)₃L₂] to react with an excess of isocyanide. Treatment of these bromocomplexes [ReBr(CO)₂(CNR)_nL₃₋_n] with SnCl₂ · 2H₂O yielded the trichlorostannyl derivatives [Re(SnCl₃)(CO)₂(CNR)_nL₃₋_n] (5–8). Trihydridestannyl complexes [Re(SnH₃)(CO)₂(CNR)_nL₃₋_n] (9–12) were prepared by allowing trichlorostannyl compounds 5–8 to react with NaBH₄ in ethanol. The trimethylstannyl derivative [Re(SnMe₃)(CO)₂(CNC₆H₄-4-CH₃){PPh(OEt)₂}₂] (13b) was also prepared by treating [Re(SnCl₃)(CO)₂(CNC₆H₄-4-CH₃){PPh(OEt)₂}₂] with an excess of MgBrMe in diethylether. Reaction of the tin trihydride complexes [Re(SnH₃)(CO)₂(CNR)_nL₃₋_n] (9–12) with CO₂ (1 atm) led to dinuclear OH-bridging bis(formate) derivatives [Re{Sn(OC(H) double bond O)₂(μ-OH)}(CO)₂(CNR)_nL₃₋_n]₂ (14, 15). The complexes were characterised spectroscopically (IR, ¹H, ³¹P, ¹³C, ¹¹⁹Sn NMR) and by X-ray crystal structure determination of [Re(SnH₃)(CO)₂{CNC(CH₃)₃}{PPh(OEt)₂}₂] (10b).

Graphical abstract

The preparation of mixed-ligand trihydridestannyl complexes [Re(SnH₃)(CO)₂(CNR)_nL₃₋_n] (n = 1, 2) with carbonyl, isocyanide and phosphite, and their spectroscopic and crystallographic characterisation, are described. Reaction of the tin hydride complexes with CO₂ leading to dinuclear OH-bridging bis(formate) derivatives [Re{Sn(OC(H) double bond O)₂(μ-OH)}(CO)₂(CNR)_nL₃₋_n]₂ is also reported.

Introduction

Transition metal complexes containing stannyl groups SnX₃ and SnR₃ as ligands have been extensively studied in recent years [1], [2], [3], not only for the variety of reactions shown both at the metal and at the tin centre, but also because the introduction of a tin ligand into the metal fragment may modify the chemical properties of the complexes and often improve their catalytic activity [1], [4].

A large number of mono- and polynuclear stannyl complexes containing halogenostannyl (SnX₃) and organostannyl (SnR₃) ligands have been synthesised [1], [2], [3]. However, despite the numerous studies, only recently stable complexes containing the simplest of the tin ligand, the trihydride SnH₃, have been prepared [5] using an osmium(II) fragment of the type [Os(Tp)L(PPh₃)] [Tp = tris(pyrazolyl)borate; L = phosphite] to stabilise the SnH₃ ligand. Further studies from our and other laboratories have pointed out that other d⁶ metal fragments, of the type [M(Cp)L(PPh₃)] (M = Ru, Os; L = phosphite), [M(CO)_nL₅₋_n] (M = Mn, Re; n = 2, 3) [5], [6] and [Os(κ²-S₂CNMe₂)(CO)(PPh₃)₂] [7], are able to stabilise the tin trihydride ligand, and that the reactivity of the SnH₃ group strongly depends on the nature of the ancillary ligands. For example, hydridebis(formate)stannyl complexes [M[SnH{OC(H) double bond O}₂](Cp)L(PPh₃)] are stable and isolable only with the Cp ligand [6c], but with [M(Tp)L(PPh₃)] or with the [M(CO)_nL₅₋_n] fragments the dinuclear OH-bridging bis(formate) derivatives [[M]–Sn{OC(H)O}₂(μ-OH)]₂ are always obtained [6](a), [6](c).

These results prompted us to extend our study to include isocyanides (CNR) as supporting ligands in the chemistry of tin hydride complexes, to test whether SnH₃ complexes can be prepared with such ligands, and how isocyanide may change the properties of the tin hydride group.

The results of these studies, which include preparation and some reactivity of unprecedented stannyl complexes of rhenium [8] stabilised by isocyanide ligands, are reported here.

Section snippets

General considerations

All synthetic work was carried out in an appropriate atmosphere (Ar) using standard Schlenk techniques or an inert atmosphere dry-box. Once isolated, the complexes were found to be relatively stable in air, but were stored under nitrogen at −25 °C. All solvents were dried over appropriate drying agents, degassed on a vacuum line, and distilled into vacuum-tight storage flasks. Re₂(CO)₁₀ was a Pressure Chemical Co. (USA) product and was used as received. Phosphite PPh(OEt)₂ was prepared by the

Preparation of isocyanide complexes

Mixed-ligand isocyanide complexes [ReBr(CO)₂(CNR)L₂] (1, 2) and [ReBr(CO)₂(CNR)₂L] (3, 4) were prepared by substituting carbonyl ligands in the [ReBr(CO)_nL₅₋_n] (n = 3, 4) precursors, as shown in Scheme 1.

Tricarbonyl complexes [ReBr(CO)₃L₂] react with isocyanide CNR in refluxing toluene to give the mixed-ligand monoisocyanide derivatives [ReBr(CO)₂(CNR)L₂] (1, 2) in good yields.

Under the same conditions, tetracarbonyl species [ReBr(CO)₄L] react with isocyanide CNR to give bis(isocyanide)

Conclusions

In this paper we report the synthesis of mixed-ligand rhenium complexes [ReBr(CO)₂(CNR)₃₋_nL_n] (n = 2, 3) with carbonyl, phosphite and isocyanide, allowing the preparation of unprecedented trihydridestannyl complexes stabilised by isocyanide ligands. Structural parameters for the tert-butyl isocyanide derivative [Re(SnH₃)(CO)₂{CNC(CH₃)₃}{PPh(OEt)₂}₂] are also reported.

Trimethylstannyl complexes [Re(SnMe₃)(CO)₂(CNC₆H₄-4-CH₃O){PPh(OEt)₂}₂] and dinuclear tin formate derivatives [Re{Sn(OC(H) double bond O)₂

Acknowledgments

We thank Daniela Baldan for her technical assistance.

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Preparation of trihydridostannyl complexes of rhenium stabilised by isocyanide ligands

Abstract

Graphical abstract

Introduction

Section snippets

General considerations

Preparation of isocyanide complexes

Conclusions

Acknowledgments

J. Am. Chem. Soc.

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