Diphosphacarborane analogues of ferrocene: the synthesis of two isomeric twelve-vertex closo-[(eta5-C5H5)FeP2CB8H9] complexes.

The reaction of the Tl+ salt of the [nido-7,8,9-P2CB8H9]- anion (1-) with [CpFe(CO)2I](Cp =eta(5)-C5H5) in refluxing mesitylene for 12 h gives mixed-sandwich [1-Cp-closo-1,2,3,4-FeP2CB8H9] (2) (yield 63%). Reaction of the PPh4+ salt of the isomeric [nido-7,8,10-P2CB8H9]- anion 3- with [CpFe(CO)2I] in refluxing mesitylene gives [1-Cp-closo-1,2,3,5-FeP2CB8H9]4 (yield 56%), isomeric with 2. Compound 4 also results (yield 92%) from the sublimation of 2 under argon at ca. 350 degrees C. The constitution of all compounds is established by mass spectrometry, IR spectroscopy and multinuclear NMR spectroscopy (1H, 11B, 31P, and 13C; two-dimensional [11B-11B]-COSY, and 1H- 11B(selective)), further confirmed in the case of 4 by a single-crystal X-ray diffraction analysis.

[1]  J. Holub,et al.  Phosphadicarbaborane Analogues of Ferrocene: New Isomers of [closo-(η5-C5H5)FePC2B8H10] , 2003 .

[2]  I. Císařová,et al.  Formation of Two Isomeric closo‐[(η5‐C5H5)FePC2B8H10] Phosphadicarbaborane Analogues of Ferrocene via Isolable η1‐Bonded Complexes of the [7‐{(η5‐C5H5)Fe(CO)2}‐(η1‐nido‐PC2B8H10)] Type , 2003 .

[3]  J. Holub,et al.  Phosphacarborane Chemistry: The Synthesis of the Parent Phosphadicarbaboranesnido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]−, and Their 10-Cl Derivatives − Analogs of the Cyclopentadienide Anion , 2002 .

[4]  C. Viňas,et al.  Unusual 9-->10 rearrangement of the substituted cage carbon in the ferratricarbollide series. Synthesis of the isomeric complexes [2-eta 5-(C5H5)-10-X-closo-2,1,7,10-FeC3B8H10] (where X = H2N, MeHN, Me2N, and ButHN). , 2000, Inorganic chemistry.

[5]  J. Kennedy,et al.  Phosphacarborane chemistry. New cluster isomers in the eleven-vertex nido-phosphadicarbaborane series: synthesis of the nido phosphadicarbaboranes 7,8,11-PC2B8H11, [7,8,11-PC2B8H10]- and 7-Ph-7,8,10-PC2B8H10 , 2000 .

[6]  I. Císařová,et al.  A Series of the Twelve-Vertex Ferratricarbollides [2-(eta(5)-C(5)H(5))-9-X-closo-2,1,7,9-FeC(3)B(8)H(10)] (Where X = H(2)N, MeHN, Me(2)N, Bu(t)()HN, Bu(t)()(Me)N). A Highly Stable Metallatricarbaborane System with Amine Functions in the Para Position to the Metal Center. , 1999, Inorganic chemistry.

[7]  P. Schleyer,et al.  Parent tricarbollides [nido-7,8,9-C3B8H11](-), nido-7,8,9-C3B8H12, [nido-7,8,10-C3B8H11](-), and their derivatives , 1997 .

[8]  W. Hutton,et al.  TWO‐DIMENSIONAL BORON‐11‐BORON‐11 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY AS A PROBE OF POLYHEDRAL STRUCTURE: APPLICATION TO BORON HYDRIDES, CARBORANES, METALLABORANES, AND METALLACARBORANES , 1984 .

[9]  W. Mcfarlane,et al.  A 13C and 31P magnetic double resonance study of organo-phosphorus compounds , 1968, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[10]  E. Becker.  Chapter 10 – Two-Dimensional NMR , 2000 .

[11]  F. Teixidor,et al.  The First Examples of Metallatricarbollides. Isomeric Twelve-Vertex Cyclopentadienyl Ferratricarbadodecaboranes [(η5-C5H5)-closo-FeC3B8H11] , 1995 .

[12]  F. Teixidor,et al.  Tricarbollides—compounds of the eleven-vertex series of tricarbaboranes , 1995 .

[13]  T. Jelínek,et al.  Selective dismantling of closo-1,2-C2B10H12 to lower-cage dicarbaborane systems , 1991 .

[14]  J. Kennedy,et al.  Identification of the endo,exo isomer of 6,9-(PMe2Ph)2-arachno-B10H12 by nuclear magnetic resonance spectroscopy , 1987 .

[15]  W. Hutton,et al.  Two-dimensional boron-11−boron-11 nuclear magnetic resonance spectroscopy as a probe of polyhedral structure: application to boron hydrides, carboranes, metallaboranes, and metallacarboranes , 1984 .