Coordination behavior of (ferrocenylethynyl)diphenylphosphane towards binuclear iron and cobalt carbonyls

Grzegorz Filipczyk, Alexander Hildebrandt, Tobias Rueffer, Marcus Korb, Heinrich Lang

Research output: Contribution to journalArticle

Abstract

The reaction of PPh2(C CFc) (Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) (1) with Fe-2(CO)(9) (2) and Co-2(CO)(8) (3) afforded Fe(CO)(4)(PPh2(C CFc)) (4), Fe(CO)(3)(PPh2(C CFc))(2) (5), Fe-2(CO)(6)(mu,eta(2)-C CFc)(rho-PPh2) (6) (reaction of 1 with 2), PPh2((eta(2)-C CFc)Co-2(CO)(6)) (7) and Co-2(CO)(7)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (8) (reaction of I with 3). Treatment of 4 with one equiv of 3 produced Fe(CO)(4)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (9). This compound was also obtained when 7 was reacted with 2. All compounds were characterized by NMR, UV-Vis and IR spectroscopy, high resolution ESI-TOF mass -spectrometry and elemental analysis. The structures of 4 and 6-8 in the solid state were determined by single crystal X-ray structure analysis. These studies verified that 1 acts as a KP-ligand to a Fe(CO)(4) fragment in 4. In 7 and 8 the C C unit is mu-kappa C:kappa C' coordinated to a Co-2(CO)(6) fragment, and additionally for 8 the PPh2 unit is datively-bonded to a Co-2(CO)(7) moiety. By the reaction of 1 with 2 at elevated temperature, the P-C bond in 1 is cleaved and hence 6 is formed in which the Ph2P unit is mu-1:2 kappa P-2 coordinated and the FcC C moiety is bonded in mu-1:2 kappa C-2(1),kappa C-2 fashion to a Fe-2(CO)(6) (Fe Fe) entity. The electronic properties of 4-6 and 9 were studied by cyclic and square -wave voltammetry. The replacement of a CO ligand in 4 with a 2nd PPh2(C CFc) ligand induces electrochemical reversibility of the Fe(CO)(3) moiety in 5. As compared to non -coordinated 1, a cathodic shift of the Fc redox potentials is characteristic for 6 and 9, respectively, whereas an anodic shift is observed for 4 and 5. (C) 2016 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)142-151
Number of pages10
JournalJournal of Organometallic Chemistry
Volume828
DOIs
Publication statusPublished - 1 Jan 2017
Externally publishedYes

Cite this

Filipczyk, Grzegorz ; Hildebrandt, Alexander ; Rueffer, Tobias ; Korb, Marcus ; Lang, Heinrich. / Coordination behavior of (ferrocenylethynyl)diphenylphosphane towards binuclear iron and cobalt carbonyls. In: Journal of Organometallic Chemistry. 2017 ; Vol. 828. pp. 142-151.
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title = "Coordination behavior of (ferrocenylethynyl)diphenylphosphane towards binuclear iron and cobalt carbonyls",
abstract = "The reaction of PPh2(C CFc) (Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) (1) with Fe-2(CO)(9) (2) and Co-2(CO)(8) (3) afforded Fe(CO)(4)(PPh2(C CFc)) (4), Fe(CO)(3)(PPh2(C CFc))(2) (5), Fe-2(CO)(6)(mu,eta(2)-C CFc)(rho-PPh2) (6) (reaction of 1 with 2), PPh2((eta(2)-C CFc)Co-2(CO)(6)) (7) and Co-2(CO)(7)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (8) (reaction of I with 3). Treatment of 4 with one equiv of 3 produced Fe(CO)(4)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (9). This compound was also obtained when 7 was reacted with 2. All compounds were characterized by NMR, UV-Vis and IR spectroscopy, high resolution ESI-TOF mass -spectrometry and elemental analysis. The structures of 4 and 6-8 in the solid state were determined by single crystal X-ray structure analysis. These studies verified that 1 acts as a KP-ligand to a Fe(CO)(4) fragment in 4. In 7 and 8 the C C unit is mu-kappa C:kappa C' coordinated to a Co-2(CO)(6) fragment, and additionally for 8 the PPh2 unit is datively-bonded to a Co-2(CO)(7) moiety. By the reaction of 1 with 2 at elevated temperature, the P-C bond in 1 is cleaved and hence 6 is formed in which the Ph2P unit is mu-1:2 kappa P-2 coordinated and the FcC C moiety is bonded in mu-1:2 kappa C-2(1),kappa C-2 fashion to a Fe-2(CO)(6) (Fe Fe) entity. The electronic properties of 4-6 and 9 were studied by cyclic and square -wave voltammetry. The replacement of a CO ligand in 4 with a 2nd PPh2(C CFc) ligand induces electrochemical reversibility of the Fe(CO)(3) moiety in 5. As compared to non -coordinated 1, a cathodic shift of the Fc redox potentials is characteristic for 6 and 9, respectively, whereas an anodic shift is observed for 4 and 5. (C) 2016 Elsevier B.V. All rights reserved.",
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author = "Grzegorz Filipczyk and Alexander Hildebrandt and Tobias Rueffer and Marcus Korb and Heinrich Lang",
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Coordination behavior of (ferrocenylethynyl)diphenylphosphane towards binuclear iron and cobalt carbonyls. / Filipczyk, Grzegorz; Hildebrandt, Alexander; Rueffer, Tobias; Korb, Marcus; Lang, Heinrich.

In: Journal of Organometallic Chemistry, Vol. 828, 01.01.2017, p. 142-151.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Coordination behavior of (ferrocenylethynyl)diphenylphosphane towards binuclear iron and cobalt carbonyls

AU - Filipczyk, Grzegorz

AU - Hildebrandt, Alexander

AU - Rueffer, Tobias

AU - Korb, Marcus

AU - Lang, Heinrich

PY - 2017/1/1

Y1 - 2017/1/1

N2 - The reaction of PPh2(C CFc) (Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) (1) with Fe-2(CO)(9) (2) and Co-2(CO)(8) (3) afforded Fe(CO)(4)(PPh2(C CFc)) (4), Fe(CO)(3)(PPh2(C CFc))(2) (5), Fe-2(CO)(6)(mu,eta(2)-C CFc)(rho-PPh2) (6) (reaction of 1 with 2), PPh2((eta(2)-C CFc)Co-2(CO)(6)) (7) and Co-2(CO)(7)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (8) (reaction of I with 3). Treatment of 4 with one equiv of 3 produced Fe(CO)(4)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (9). This compound was also obtained when 7 was reacted with 2. All compounds were characterized by NMR, UV-Vis and IR spectroscopy, high resolution ESI-TOF mass -spectrometry and elemental analysis. The structures of 4 and 6-8 in the solid state were determined by single crystal X-ray structure analysis. These studies verified that 1 acts as a KP-ligand to a Fe(CO)(4) fragment in 4. In 7 and 8 the C C unit is mu-kappa C:kappa C' coordinated to a Co-2(CO)(6) fragment, and additionally for 8 the PPh2 unit is datively-bonded to a Co-2(CO)(7) moiety. By the reaction of 1 with 2 at elevated temperature, the P-C bond in 1 is cleaved and hence 6 is formed in which the Ph2P unit is mu-1:2 kappa P-2 coordinated and the FcC C moiety is bonded in mu-1:2 kappa C-2(1),kappa C-2 fashion to a Fe-2(CO)(6) (Fe Fe) entity. The electronic properties of 4-6 and 9 were studied by cyclic and square -wave voltammetry. The replacement of a CO ligand in 4 with a 2nd PPh2(C CFc) ligand induces electrochemical reversibility of the Fe(CO)(3) moiety in 5. As compared to non -coordinated 1, a cathodic shift of the Fc redox potentials is characteristic for 6 and 9, respectively, whereas an anodic shift is observed for 4 and 5. (C) 2016 Elsevier B.V. All rights reserved.

AB - The reaction of PPh2(C CFc) (Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) (1) with Fe-2(CO)(9) (2) and Co-2(CO)(8) (3) afforded Fe(CO)(4)(PPh2(C CFc)) (4), Fe(CO)(3)(PPh2(C CFc))(2) (5), Fe-2(CO)(6)(mu,eta(2)-C CFc)(rho-PPh2) (6) (reaction of 1 with 2), PPh2((eta(2)-C CFc)Co-2(CO)(6)) (7) and Co-2(CO)(7)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (8) (reaction of I with 3). Treatment of 4 with one equiv of 3 produced Fe(CO)(4)(PPh2((eta(2)-C CFc)Co-2(CO)(6))) (9). This compound was also obtained when 7 was reacted with 2. All compounds were characterized by NMR, UV-Vis and IR spectroscopy, high resolution ESI-TOF mass -spectrometry and elemental analysis. The structures of 4 and 6-8 in the solid state were determined by single crystal X-ray structure analysis. These studies verified that 1 acts as a KP-ligand to a Fe(CO)(4) fragment in 4. In 7 and 8 the C C unit is mu-kappa C:kappa C' coordinated to a Co-2(CO)(6) fragment, and additionally for 8 the PPh2 unit is datively-bonded to a Co-2(CO)(7) moiety. By the reaction of 1 with 2 at elevated temperature, the P-C bond in 1 is cleaved and hence 6 is formed in which the Ph2P unit is mu-1:2 kappa P-2 coordinated and the FcC C moiety is bonded in mu-1:2 kappa C-2(1),kappa C-2 fashion to a Fe-2(CO)(6) (Fe Fe) entity. The electronic properties of 4-6 and 9 were studied by cyclic and square -wave voltammetry. The replacement of a CO ligand in 4 with a 2nd PPh2(C CFc) ligand induces electrochemical reversibility of the Fe(CO)(3) moiety in 5. As compared to non -coordinated 1, a cathodic shift of the Fc redox potentials is characteristic for 6 and 9, respectively, whereas an anodic shift is observed for 4 and 5. (C) 2016 Elsevier B.V. All rights reserved.

KW - Iron carbonyl

KW - Cobalt carbonyl

KW - Phospinoacetylide

KW - Electrochemistry

KW - Solid state structure

KW - CROSS-COUPLING REACTIONS

KW - DICOBALT OCTACARBONYL

KW - CRYSTAL-STRUCTURES

KW - FERROCENYLETHYNYL PHOSPHANES

KW - STRUCTURAL-CHARACTERIZATION

KW - NONAQUEOUS SOLVENTS

KW - MOCVD PRECURSOR

KW - METAL-COMPLEXES

KW - PHOSPHINE

KW - REACTIVITY

U2 - 10.1016/j.jorganchem.2016.11.034

DO - 10.1016/j.jorganchem.2016.11.034

M3 - Article

VL - 828

SP - 142

EP - 151

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -