Carbon−Phosphorus Bond Activation of Tri(2-thienyl)phosphine at Dirhenium and Dimanganese Centers

Authors

Md. Nazim Uddin, Jahangirnagar UniversityFollow
M. Abdul Mottalib, Lund University
Noorjahan Begum, Lund University
Shishir Ghosh, Jahangirnagar UniversityFollow
Arun K. Raha, Jahangirnagar University
Daniel T. Haworth, Marquette UniversityFollow
Sergey V. Lindeman, Marquette UniversityFollow
Tasneem Siddiquee, University of Wisconsin - MilwaukeeFollow
Dennis W. Bennett, University of Wisconsin - MilwaukeeFollow
Graeme Hogarth, University College London
Ebbe Nordlander, Lund University
Shariff E. Kabir, Jahangirnagar University

Document Type

Article

Language

eng

Publication Date

2009

Publisher

American Chemical Society

Source Publication

Organometallics

Source ISSN

0276-7333

Abstract

Reaction of [Re₂(CO)₉(NCMe)] with tri(2-thienyl)phosphine (PTh₃) in refluxing cyclohexane affords three substituted dirhenium complexes: [Re₂(CO)₉(PTh₃)] (1), [Re₂(CO)₈(NCMe)(PTh₃)] (2), and [Re₂(CO)₈(PTh₃)₂] (3). Complex 2 was also obtained from the room-temperature reaction of [Re₂(CO)₈(NCMe)₂] with PTh₃ and is an unusual example in which the acetonitrile and phosphine ligands are coordinated to the same rhenium atom. Thermolysis of 1 and 3 in refluxing xylene affords [Re₂(CO)₈(μ-PTh₂)(μ-η¹:κ¹-C₄H₃S)] (4) and [Re₂(CO)₇(PTh₃)(μ-PTh₂)(μ-H)] (5), respectively, both resulting from carbon−phosphorus bond cleavage of a coordinated PTh₃ ligand. Reaction of [Re₂(CO)₁₀] and PTh₃ in refluxing xylene gives a complex mixture of products. These products include 3−5, two further binuclear products, [Re₂(CO)₇(PTh₃)(μ-PTh₂)(μ-η¹:κ¹-C₄H₃S)] (6) and [Re₂(CO)₇(μ-κ¹:κ²-Th₂PC₄H₂SPTh)(μ-η¹:κ¹-C₄H₃S)] (7), and the mononuclear hydrides [ReH(CO)₄(PTh₃)] (8) and trans-[ReH(CO)₃(PTh₃)₂] (9). Binuclear 6 is structurally similar to 4 and can be obtained from reaction of the latter with 1 equiv of PTh₃. Formation of 7 involves a series of rearrangements resulting in the formation of a unique new diphosphine ligand, Th₂PC₄H₂SPTh. Reaction of [Mn₂(CO)₁₀] with PTh₃ in refluxing toluene affords the phosphine-substituted product [Mn₂(CO)₉(PTh₃)] (10) and two carbon−phosphorus bond cleavage products, [Mn₂(CO)₆(μ-PTh₂)(μ-η¹:η⁵-C₄H₃S)] (11) and [Mn₂(CO)₅(PTh₃)(μ-PTh₂)(μ-η¹:η⁵-C₄H₃S)] (12). Both 11 and 12 contain a bridging thienyl ligand that is bonded to one manganese atom in a η⁵-fashion. The molecular structures of eight of these new complexes were established by single-crystal X-ray diffraction studies, allowing a detailed analysis of the disposition of the coordinated ligands.

Comments

Accepted version. Organometallics, Vol. 28, No. 5 (2009): 1514-1523. DOI. © 2009 American Chemical Society. Used with permission.

Recommended Citation

Uddin, Md. Nazim; Mottalib, M. Abdul; Begum, Noorjahan; Ghosh, Shishir; Raha, Arun K.; Haworth, Daniel T.; Lindeman, Sergey V.; Siddiquee, Tasneem; Bennett, Dennis W.; Hogarth, Graeme; Nordlander, Ebbe; and Kabir, Shariff E., "Carbon−Phosphorus Bond Activation of Tri(2-thienyl)phosphine at Dirhenium and Dimanganese Centers" (2009). Chemistry Faculty Research and Publications. 611.
https://epublications.marquette.edu/chem_fac/611