Structurally diverse Rh(i) and Mn(i) complexes derived from the new ambidentate indene ligand, (1-{iPr2P(S)}-2-{NMe2})C9H6

Wechsler, Dominik; McDonald, Robert; Ferguson, Michael J.; Stradiotto, Mark

doi:10.1039/b410328a

Cited by 13 publications

(19 citation statements)

References 16 publications

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“…In light of our previous observation that treatment of BrMn(CO) 5 with 1a[Li] resulted in a complex distribution of products, an alternative synthetic strategy starting from the corresponding phosphine sulfide 1b[H] was explored (Scheme ). Lithiation of 1b[H] followed by treatment with BrMn(CO) 5 led to the clean formation of 2a , which was isolated as an analytically pure solid in 96% yield …”

Section: Resultsmentioning

confidence: 99%

New Racemic Planar-Chiral Metalloligands Derived from Donor-Substituted Indenes: A Synthetic, Structural, and Catalytic Investigation

et al. 2007

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The synthesis and characterization of a new family of (η5-indenyl)MLn complexes (MLn = Mn(CO)3, Cp*Ru, or Cp*Fe; Cp* = η5-C5Me5) derived from 3-P i Pr2-indene, 1-P i Pr2-2-NMe2-indene (1a[H]), or 1-P(S) i Pr2-2-NMe2-indene (1b[H]) are described. Lithiation of 1b[H] followed by treatment with BrMn(CO)5, 0.25 equiv of [Cp*RuCl]4, or Cp*Li/FeCl2 provided the corresponding (η5-1b)MLn complexes (MLn = Mn(CO)3, 2a, 96%; Cp*Ru, 2b, 87%; or Cp*Fe, 2c, 55%). Similarly, treatment of 1a[Li] with 0.25 equiv of [Cp*RuCl]4 or Cp*Li/FeCl2 provided the corresponding (η5-1a)MLn complexes (MLn = Cp*Ru, 3b, 74%; or Cp*Fe, 3c, 62%). Whereas combination of 3b and 0.5 equiv of [(COD)RhCl]2 afforded [(COD)Rh(κ2-P,N-3b)]+Cl- ([4b] + Cl - ; 49% isolated yield), under similar conditions 3c was observed to undergo a decomposition reaction resulting in the formation of the zwitterionic complex (COD)Rh(κ2-P,N-1a) (5; COD = η4-1,5-cyclooctadiene). Each of 3a−c was observed to react cleanly with [(COD)Rh(THF)2]+BF4 - (prepared in situ) to give the corresponding [(COD)Rh(κ2-P,N-3a−c)]+BF4 - complex ([4a − c] + BF 4 - ; 87%, 96%, and 89% isolated yield, respectively). Whereas lithiation of 3-P i Pr2-indene followed by the addition of BrMn(CO)5 generated a complex mixture of products, similar reactions employing 0.25 equiv of [Cp*RuCl]4 or Cp*Li/FeCl2 afforded 6b or 6c in 98% and 43% yield, respectively. Treatment of 6b with 0.5 equiv of [(COD)RhCl]2 allowed for the isolation of (COD)RhCl(κ1-P-6b) 7 in 96% isolated yield. Each of [4a − c] + BF 4 - proved to be an active catalyst for addition of pinacolborane to styrene, with the observed regioselectivity being dependent on the nature of the η5-coordinated metal fragment, as well as the solvent employed. Single-crystal X-ray diffraction data for 2a, 2b, 2c, 3b, [4c] + BF 4 - , and 7 are provided.

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Section: Resultsmentioning

confidence: 99%

New Racemic Planar-Chiral Metalloligands Derived from Donor-Substituted Indenes: A Synthetic, Structural, and Catalytic Investigation

et al. 2007

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“…5a), one planar with both C … O = 3.48 Å , and the other twisted by 18.8u and with both C … O = 3.45 Å . 6a), 39 shows a strong antiparallel motif (IV) with C … O = 3.04 Å , A1 = 73.1u and A2 = 106.9u, which is reinforced by a symmetrical pair of perpendicular C … O contacts of 3.46 Å in a motif (V) which has A1 = 85.8u and A4 = 145.2u. 5b.…”

Section: Examples Of Co … Co Interactions In Tr-clo Structuresmentioning

confidence: 99%

“…Thus, the tricarbonylmanganese compound BIMLIT (Fig. 6a), 39 shows a strong antiparallel motif (IV) with C … O = 3.04 A ˚, A1 = 73.1u and A2 = 106.9u, which is reinforced by a symmetrical pair of perpendicular C … O contacts of 3.46 A ˚in a motif (V) which has A1 = 85.8u and A4 = 145.2u. Involvement of the antiparallel motif (IV) in the formation of extended structures is also common, as illustrated in Fig.…”

Section: Examples Of Co … Co Interactions In Tr-clo Structuresmentioning

confidence: 99%

Carbonyl⋯carbonyl interactions in first-row transition metal complexes

et al. 2006

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Carbonyl … carbonyl interactions involving Tr-CLO moieties (Tr = first-row transition element) have been studied using crystal structure data retrieved from the Cambridge Structural Database and by use of DFT calculations. By comparison with organic ketones, Tr-CLO systems show an increased tendency to form close CO … CO interactions, with 45% of these forming pairwise interactions in a sheared antiparallel dimer motif and 55% having a perpendicular (single interaction) geometry. The bulky Tr and steric hindrance arising from other ligands at Tr play a significant role in the formation and geometry of the interactions. DFT calculations for the antiparallel dimer indicate that interaction energies for Tr-CLO systems are slightly stronger than for organic ketones, and there is evidence of a stronger CLO bond dipole in Tr-CLO systems. With interaction energies comparable to those for medium strength hydrogen bonds, we conclude that CO … CO interactions in Tr-CLO species may have a role to play in the design of novel carbonyl-containing inorganic and metal-organic structures.

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“…With the goal of identifying new classes of transition metal complexes that are capable of mediating synthetically useful chemical transformations, we have recently initiated a research program focused on exploring the coordination behavior and reactivity properties of complexes supported by new ligands derived from 2-dimethylaminoindene ( 1 [H]), including the “P,N” ligands 2 [H] and 2 ‘[H], as well as the “P(S),N” ligand, 3 [H] (Scheme ) . These new multifunctional ligands strategically incorporate hard and soft donor fragments fused to an unsaturated carbocyclic backbone, in anticipation that such a combination of chemically diverse donor groups will allow for the binding of a range of metal fragments, as well as allowing for the rational construction of heteropolynuclear metal complexes …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Crystallographic Characterization of New Manganese(I) Complexes of Donor-Functionalized Indenes

et al. 2005

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Treatment of 1-P i Pr2-2-NMe2-indene (2[H]) with BrMn(CO)5 provided κ2-P,N-(2-NMe2-3-P i Pr2-indene)Mn(CO)3Br (4) in 73% yield. Addition of either AgBF4 or AgSO3CF3 to 4 yielded the corresponding inner-sphere tetrafluoroborate (5a) and triflate (5b) complexes in 62% and 65% yield, respectively. Deprotonation of 4, 5a, or 5b produced an intractable mixture of products. The cationic complex [κ2-P,N-(2-NMe2-3-P i Pr2-indene)Mn(CO)4]+BF4 - (6) was prepared in 30% yield by treating BrMn(CO)5 with AgBF4, followed by the addition of 2[H]. The benzocymantrene η5-[2]Mn(CO)3 was prepared in 56% yield via reduction of η5-(2-NMe2-3-P(S) i Pr2-indenyl)Mn(CO)3 with Cl3SiSiCl3. Compound 2[Li] reacts with BrMn(CO)5 to give a complex product mixture, from which 4 and [κ2-P,N-(2-NMe2-3-P i Pr2-indene)Mn(CO)4]+[Mn2(CO)8(μ-P i Pr2)]- (7) were isolated. 2-Dimethylaminoindene (1[H]) was silylated to give 1-SiMe3-2-NMe2-indene (8[H]) in 93% yield. Treatment of 8[Li] with ClP i Pr2, followed by the addition of BrMn(CO)5, afforded κ2-P,N-(1-SiMe3-2-NMe2-3-P i Pr2-indene)Mn(CO)3Br (10) in 27% yield. Alternatively, addition of 8[Li] to BrMn(CO)5 followed by the addition of ClP i Pr2 generated a mixture of products, from which the substituted 1,1‘-biindene rac-(2-NMe2-3-SiMe3-C9H5)2 (rac-12) was isolated. Treatment of 1[Li] with BrMn(CO)5 provided η5-(2-NMe2-indenyl)Mn(CO)3 (11) in 41% yield. Single-crystal X-ray diffraction data for 4·0.5C7H8, 5a·0.5C7H8, 5b, 6, η5-[2]Mn(CO)3, 7·0.5C7H8, 10, 11, and rac-12 are reported.

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Structurally diverse Rh(i) and Mn(i) complexes derived from the new ambidentate indene ligand, (1-{iPr2P(S)}-2-{NMe2})C9H6

Cited by 13 publications

References 16 publications

New Racemic Planar-Chiral Metalloligands Derived from Donor-Substituted Indenes: A Synthetic, Structural, and Catalytic Investigation

New Racemic Planar-Chiral Metalloligands Derived from Donor-Substituted Indenes: A Synthetic, Structural, and Catalytic Investigation

Carbonyl⋯carbonyl interactions in first-row transition metal complexes

Synthesis and Crystallographic Characterization of New Manganese(I) Complexes of Donor-Functionalized Indenes

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