Preparation and reactivity of stannyl and germyl complexes of cobalt

doi:10.1016/j.jorganchem.2012.07.045

Journal of Organometallic Chemistry

Volume 718, 1 November 2012, Pages 108-116

https://doi.org/10.1016/j.jorganchem.2012.07.045 Get rights and content

Abstract

Trichlorostannyl complex Co(SnCl₃)(CO)₂(PPh₃)₂ (1) was prepared by allowing the chloro compound CoCl(CO)₂(PPh₃)₂ to react with SnCl₂·2H₂O. Instead, treatment of the iodo complex CoI(CO)₂[PPh(OEt)₂]₂ with SnCl₂·2H₂O afforded a mixture of Co(SnCl₂I)(CO)₂[PPh(OEt)₂]₂ (2a) and Co(SnCl₃)(CO)₂[PPh(OEt)₂]₂ (2b) derivatives. Trichlorogermyl complexes Co(GeCl₃)(CO)₂L₂ (3, 4) [L = PPh₃, PPh(OEt)₂] were prepared by allowing halo compounds CoX(CO)₂L₂ (X = Cl, I) to react with GeCl₂·dioxane. Treatment of trihalostannyl complexes Co(SnCl₂X)(CO)₂L₂ (1, 2) (X = Cl, I) with NaBH₄ in ethanol yielded tin trihydrido derivatives Co(SnH₃)(CO)₂L₂ (5, 6). Instead, reaction of Co(SnCl₂X)(CO)₂[PPh(OEt)₂]₂ (2) with LiAlH₄ in THF yielded the hydrido CoH(CO)₂[PPh(OEt)₂]₂ (7). Trimethylstannyl Co(SnMe₃)(CO)₂L₂ (8, 9) and trialkynylstannyl derivatives Co[Sn(C triple bond CPh)₃](CO)₂L₂ (10, 11) were prepared by allowing trihalostannyl compounds Co(SnCl₂X)(CO)₂L₂ (1, 2) to react with MgBrMe and with Li⁺(PhCC)⁻, respectively, in THF. The complexes were characterised by spectroscopy (IR and ¹H, ³¹P, ¹³C, ¹¹⁹Sn NMR) and by X-ray crystal structure determination of Co(SnCl₂X)(CO)₂[PPh(OEt)₂]₂ (2) and Co(GeCl₃)(CO)₂[PPh(OEt)₂]₂ (4).

Graphical abstract

Reaction of halocomplexes CoX(CO)₂L₂ with SnCl₂·2H₂O and GeCl₂·dioxane leading to trihalostannyl Co(SnCl₂X)(CO)₂L₂ and trichlorogermyl derivatives Co(GeCl₃)(CO)₂L₂ is described. The preparation of trihydridostannyl complexes Co(SnH₃)(CO)₂L₂ and organostannyl derivatives Co(SnMe₃)(CO)₂L₂ and Co[Sn(C≡CPh)₃](CO)₂L₂ is also reported.

Highlights

► Synthesis of trihalo- stannyl and germyl complexes of cobalt. ► Treatment with NaBH₄ affords trihydridostannyl derivatives. ► Trimethylstannyl and trialkynylstannyl complexes of Co(I) were also prepared.

Introduction

Stannyl complexes of transition metals continue to be studied not only from a fundamental point of view [1], [2], [3], but also because the introduction of a stannyl ligand often changes the properties of the complexes and may modify the activity of noble metal catalysts [4].

Another reason for interest in stannyl complexes stems from the variety of reactions they may undergo, including ligand substitution at the tin centre, to yield stannyl complexes with novel functionalities [1], [2], [3].

We are interested in the chemistry of stannyl complexes of transition metals and have reported the synthesis and reactivity of trihydridostannyl [M]–SnH₃ and triorganostannyl [M]–SnR₃ derivatives [R = Me, C(OOMe)=CH₂, C triple bond CPh] of manganese [5] and iron [6] triads stabilised by several ligands, including CO, PR₃, P(OR)₃, η⁵-C₅H₅, tris(pyrazolyl)borate (Tp) and p-cymene.

The interesting properties shown by both trichloro- [M]–SnCl₃ and trihydridostannyl [M]–SnH₃ ligands in these complexes prompted us to extend study to cobalt, as the chemistry of stannyl complexes [7] is less well developed than that of other metals [1], [2], [3]: our aim was to test whether cobalt fragments can also stabilise trihydridostannyl derivatives. The results, which included the preparation of the first trihydridostannyl complex of cobalt, are reported here.

Section snippets

General comments

All synthetic work was carried out in an appropriate atmosphere (Ar, N₂) using standard Schlenk techniques or a vacuum atmosphere dry-box. All solvents were dried over appropriate drying agents, degassed on a vacuum line, and distilled into vacuum-tight storage flasks. Anhydrous CoI₂ and CoCl₂ were Alfa Aesar (USA) products, used as received. GeCl₂·dioxane, anhydrous SnCl₂, SnCl₂·2H₂O and CoCl₂·6H₂O were Aldrich products, used as received. Phosphite PPh(OEt)₂ was prepared by the method of

Preparation of stannyl and germyl complexes

The chlorodicarbonyl complex CoCl(CO)₂(PPh₃)₂ was reacted with SnCl₂·2H₂O in ethanol to give the trichlorostannyl derivative Co(SnCl₃)(CO)₂(PPh₃)₂ (1), which was isolated as a yellow solid and characterised (Scheme 1).

The reaction proceeded with the insertion of SnCl₂ into the Co–Cl bond, yielding trichlorostannyl derivative 1. Anhydrous SnCl₂ in dichloromethane may also be used as a reagent with CoCl(CO)₂(PPh₃)₂, affording 1 in good yields.

The reaction of the related iodo-derivative CoI(CO)₂

Conclusions

This paper demonstrates that the dicarbonyl diphosphine fragment Co(CO)₂L₂ can stabilise not only trihalostannyl [Co]–SnCl₂X (X = Cl, I) and trichlorogermyl [Co]–GeCl₃ derivatives, but also the first cobalt complexes Co(SnH₃)(CO)₂L₂ containing tin trihydrido as a ligand. Substitution of halide in Co(SnCl₂X)(CO)₂L₂ species allowed new methylstannyl Co(SnMe₃)(CO)₂L₂ and alkynylstannyl derivatives Co[Sn(C triple bond CPh)₃](CO)₂L₂ to be prepared. Crystal structure of both trichlorogermyl and trihalostannyl

Acknowledgement

The financial support of the Ministero dell'Istruzione, dell'Università e della Ricerca (MIUR, Rome), Programmi di Ricerca Scientifica di Rilevante Interesse Nazionale - PRIN 2009 is gratefully acknowledged. We thank Mrs. Daniela Baldan, from the Università Ca' Foscari Venezia, for her technical assistance.

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Preparation and reactivity of stannyl and germyl complexes of cobalt

Abstract

Graphical abstract

Highlights

Introduction

Section snippets

General comments

Preparation of stannyl and germyl complexes

Conclusions

Acknowledgement

Chem. Rev.

Coord. Chem. Rev.

Organometallics

Organometallics

Organometallics

Organometallics

Organometallics

Eur. J. Inorg. Chem.

Proc. Natl. Acad. Sci.

Dalton Trans.

Organometallics

J. Organomet. Chem.

Chem. Commun.

Dalton Trans.

Z. Naturforsch

Organometallics

Chem. Commun.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Organometallics

Inorg. Chem.

J. Am. Chem. Soc.

Inorg. Chem.

Platinum Metals Rev.

J. Catal.

J. Appl. Catal. A

Acc. Chem. Rev.

Science

Langmuir

Angew. Chem. Int. Ed.

Organometallics

Organometallics

Organometallics

Inorg. Chim. Acta

J. Organomet. Chem.

Organometallics

Dalton Trans.

Organometallics

Organometallics

Organometallics

J. Cluster Sci.

Organometallics

J. Organomet. Chem.

J. Organomet. Chem.

Inorg. Chem.

Inorg. Chem.

J. Am. Chem. Soc.

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

J. Am. Chem. Soc.

J. Org. Chem.

Inorg. Chim. Acta

Inorg. Chem.

Inorg. Chem.

SMART Version 5.054, Instrument Control and Data Collection Software

SAINT Version 6.01, Data Integration Software Package