www.elsevier.nl/locate/jorganchem Journal of Organometallic Chemistry 584 (1999) 390 – 395 Synthesis and reactivity of [(R 1 R 2 N) 2 PH]Fe(CO) 4 complexes. X-ray crystal structure of [(Ph 2 N) 2 PH]Fe(CO) 4  Jean-Jacques Brunet, Remi Chauvin, Ousmane Diallo, Bruno Donnadieu, Joe ¨lle Jaffart, Denis Neibecker * Laboratoire de Chimie de Coordination du CNRS, Unite ´ No 8241, lie ´e par conentions a `l’Uniersite ´ Paul Sabatier et a `l’Institut National Polytechnique, 205 route de Narbonne, F -31077 Toulouse, Cedex 4, France Received 13 March 1998; received in revised form 29 May 1998 Abstract KHFe(CO) 4 reacts with tris(amino)phosphines by substitution at phosphorus leading to [bis(amino)phosphine]tetracarbonyliron complexes [(R 1 R 2 N) 2 PH]Fe(CO) 4 . The X-ray structure has been determined for R 1 =R 2 =Ph. Deprotonation of these complexes with KH affords stable potassium phosphidotetracarbonylferrates which can be alkylated or acylated at phosphorus. © 1999 Elsevier Science S.A. All rights reserved. Keywords: Aminophosphines; Iron carbonyl; Hydridotetracarbonylferrates; Phosphidotetracarbonylferrates 1. Introduction As part of our interest in the chemistry of hydridote- tracarbonylferrates M + [HFe(CO) 4 ] - [1], we have re- ported the reaction of K + [HFe(CO) 4 ] - with phosphites and phosphines [2]. These reactions proceed by CO exchange processes [3], providing highly selective routes to a large variety of ionic and neutral phos- phane-substituted ironcarbonyl complexes [4 – 6]. In contrast, the reaction of K + [HFe(CO) 4 ] - with tris(dimethylamino)phosphine does not proceed by CO substitution. Instead, substitution of an amino group at phosphorus is observed, affording K 2 Fe(CO) 4 and the neutral irontetracarbonyl complex [(Me 2 N) 2 PH]- Fe(CO) 4 [7]. This reaction provides a very easy, labora- tory-scale preparation of the Collman type reagents M 2 Fe(CO) 4 (M =Na, K) for immediate use. It should also be an easy way to prepare ironcarbonyl-stabilized secondary bis(amino)phosphines. We report here the synthesis of several of these complexes and the X-ray crystal structure of [(Ph 2 N) 2 PH]Fe(CO) 4 , which is the first X-ray crystal structure of a bis(amino)phosphine coordinated to a transition metal, along with preliminary results on both the deprotonation of [(R 2 N) 2 PH]Fe(CO) 4 derivatives and the reactivity of the resulting phosphidotetracar- bonylferrate complexes. 2. Results and discussion 2.1. Synthesis of [(R 1 R 2 N) 2 PH]Fe(CO) 4 complexes The reaction of KHFe(CO) 4 1 with tris- (amino)phosphines 2a–c is conducted at room tempera-  PII of original article S0022-328X(98)00074-4X. * Corresponding author. Tel.: +33 561 333195; fax: +33 561 553003; e-mail: neibeker@lcctoul.lcc-toulouse.fr. 0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved. PII:S0022-328X(99)00031-5