Elsevier

Polyhedron

Volume 169, 1 September 2019, Pages 78-83
Polyhedron

Preparation and crystal structure of the boranehydrazine complex [RuCl(κ1-NH2NH2BPh3){P(OEt)3}4]BPh4

https://doi.org/10.1016/j.poly.2019.04.044Get rights and content

Abstract

Unlike what was previously reported, the reaction of the hydrazine derivative [Ru(NH2NH2)2{P(OEt)3}4](BPh4)2 with p-tolyldiazonium tetrafluoroborate in CH2Cl2 afforded the boranehydrazine complex [RuCl(κ1-NH2NH2BPh3){P(OEt)3}4]BPh4. The complex was characterised spectroscopically (IR and NMR) and by X-ray crystal structure determination.

Graphical abstract

The reaction of bis(hydrazine) complexes with [ArN2]+BF4 affording a boranehydrazine derivative is described.

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Introduction

Due to our longstanding interest in the chemistry of diazo complexes of transition metals we have reported on the synthesis and reactivity of hydrazine, diazene, diazenide and diazoalkane derivatives of the manganese and iron triads [1], [1](a), [1](b), [1](c), [1](d), [1](e), [1](f), [1](g), [2], [2](a), [2](b), [2](c), [2](d), [2](e), [2](f), [3], [3](a), [3](b), [3](c), [3](d), [3](e), [3](f), [3](g), [3](h). In particular, in a previous paper [4] we reported on the reactivity of bis(hydrazine) complexes [M(NH2NH2)2L4](BPh4)2 [M = Ru, Os; L = P(OEt)3] with aryldiazonium cations [ArN2]BF4 which, depending on the experimental conditions, afforded either bis(amine) [M(NH3)2L4](BPh4)2 or bis(hydrazone) derivatives [M{NH2N = C(CH3)2}2L4](BPh4)2. In the case of ruthenium, the reaction in dichloromethane gave a different compound characterised as a chloro-amine derivative [RuCl(NH3)L4]BPh4. The unusual presence of the chloro ligand prompted us to deepen our study until suitable crystals for X-ray determination were obtained. Surprisingly, the compound resulted to be a boranehydrazine derivative having formula [RuCl(κ1-NH2NH2BPh3){P(OEt)3}4]BPh4 instead of the formerly hypothesised chloro-amine species. The results of this study, which involve the preparation and the X-ray crystal structure determination of the first example of a triphenylboranehydrazine derivative, are reported here.

Section snippets

Experimental

General comments. Synthetic techniques, solvents and reagents, IR and NMR instruments were previously described [4].

Synthesis of complexes. The precursor compound [Ru(NH2NH2)2{P(OEt)3}4](BPh4)2 was prepared following the reported method [5].

[RuCl(κ1-NH2NH2BPh3){P(OEt)3}4]BPh4 (1). In a 25-mL three-necked round-bottomed flask were placed 200 mg (0.14 mmol) of [Ru(NH2NH2)2{P(OEt)3}4](BPh4)2, an excess p-tolyldiazonium salt [4-CH3C6H4N2]BF4 (0.3 mmol, 62 mg) and 15 mL of CH2Cl2. The reaction

Results and discussion

The bis(hydrazine) complex [Ru(NH2NH2)2{P(OEt)3}4](BPh4)2 reacts in CH2Cl2 with an excess of aryldiazonium cation to give the triphenylboranehydrazine derivative [RuCl(κ1-NH2NH2BPh3)-{P(OEt)3}4]BPh4 (1) which was isolated as a white solid and characterised (Scheme 1).

The formation of complex 1 is unexpected and surprising and the presence either of the completely new ligand NH2NH2BPh3 or even of the chloride are rather difficult to explain. The reaction of the bis(hydrazine) complex with

Acknowledgments

CACTI (University of Vigo) is recognized for X-ray data collection The technical support of Daniela Baldan, of the Università Ca' Foscari Venezia (Italy), is also gratefully acknowledged.

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