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Carbon-Phosphorus Bond Activation of Tri(2-thienyl)phosphine at Dirhenium and Dimanganese Centers
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Uddin, Md. Nazim (author)
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- Mottalib, Abdul (author)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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Begum, Noorjahan (author)
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Ghosh, Shishir (author)
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Raha, Arun K. (author)
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Haworth, Daniel T. (author)
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Lindeman, Sergey V. (author)
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Siddiquee, Tasneem A. (author)
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Bennett, Dennis W. (author)
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Hogarth, Graeme (author)
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Nordlander, Ebbe (author)
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Kabir, Shariff E. (author)
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(creator_code:org_t)
- 2009-02-11
- 2009
- English.
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In: Organometallics. - : American Chemical Society (ACS). - 1520-6041 .- 0276-7333. ; 28:5, s. 1514-1523
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Abstract
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- Reaction of [Re-2(CO)(9)(NCMe)] with tri(2-thienyl)phosphine (PTh3) in refluxing cyclohexane affords three substituted dirhenium complexes: [Re-2(CO)(9)(PTh3)] (1), [Re-2(CO)(8)(NCMe)(PTh3)] (2), and [Re-2(CO)(8)(PTh3)(2)] (3). Complex 2 was also obtained from the room-temperature reaction of [Re-2(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 [Re-2(CO)(8)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (4) and [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-H)] (5), respectively, both resulting from carbon-phosphorus bond cleavage of a coordinated PTh3 ligand. Reaction of [Re-2(CO)10] and PTh3 in refluxing xylene gives a complex mixture of products. These products include 3-5, two further binuclear products, [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (6) and [Re-2(CO)(7)(mu-kappa(1):kappa(2)-Th2PC4H2SPTh)(mu-eta(1):kappa(1)-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 [Mn-2(CO)(10)] with PTh3 in refluxing toluene affords the phosphine-substituted product [Mn-2(CO)(9)(PTh3)] (10) and two carbon-phosphorus bond cleavage products, [Mn-2)(CO)(6)(mu-PTh2)(mu-eta(1):eta(5)-C4H3S)] (11) and [Mn-2(CO)(5)(PTh3)(mu-PTh2)(mu-PTh2)(mu-eta(1):eta(5)-C4H3S)] (12). Both 11 and 12 contain a bridging thienyl ligand that is bonded to one manganese atom in a eta(5)-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.
Subject headings
- NATURVETENSKAP -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)
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- art (subject category)
- ref (subject category)
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Uddin, Md. Nazim
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Mottalib, Abdul
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Begum, Noorjahan
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Ghosh, Shishir
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Raha, Arun K.
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Haworth, Daniel ...
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show more...
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Lindeman, Sergey ...
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Siddiquee, Tasne ...
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Bennett, Dennis ...
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Hogarth, Graeme
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Nordlander, Ebbe
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Kabir, Shariff E ...
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Atom and Molecul ...
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Organometallics
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Lund University