Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes

James T Moore, Sudipta Chatterjee, Maxime Tarrago, Laura J. Clouston, Stephen Sproules, Eckhard Bill, Varinia Bernales, Laura Gagliardi, Shengfa Ye, Kyle M. Lancaster, Connie C Lu

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Abstract

Previously, we reported the synthesis of Ti[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ] and the Fe-Ti complex, FeTi[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc + ), respectively. Two isostructural redox members, [FeTiL] + and [FeTiL] - (2 ox and 2 red , respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL] + complex (1 ox ). The solid-state structures of the [FeTiL] +/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57 Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL] +,0,- series are primarily Fe-based and that the polarized Fe-Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).

Original languageEnglish (US)
Pages (from-to)6199-6214
Number of pages16
JournalInorganic Chemistry
Volume58
Issue number9
DOIs
StatePublished - May 6 2019

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flexibility
Density functional theory
Metals
density functional theory
X ray absorption spectroscopy
fetuses
synthesis
metals
Cyclic voltammetry
Electronic structure
Carrier concentration
Paramagnetic resonance
absorption spectroscopy
Nuclear magnetic resonance
electronic structure
solid state
Oxidation
nuclear magnetic resonance
oxidation
radii

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Moore, J. T., Chatterjee, S., Tarrago, M., Clouston, L. J., Sproules, S., Bill, E., ... Lu, C. C. (2019). Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes. Inorganic Chemistry, 58(9), 6199-6214. https://doi.org/10.1021/acs.inorgchem.9b00442

Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes. / Moore, James T; Chatterjee, Sudipta; Tarrago, Maxime; Clouston, Laura J.; Sproules, Stephen; Bill, Eckhard; Bernales, Varinia; Gagliardi, Laura; Ye, Shengfa; Lancaster, Kyle M.; Lu, Connie C.

In: Inorganic Chemistry, Vol. 58, No. 9, 06.05.2019, p. 6199-6214.

Research output: Contribution to journalArticle

Moore, JT, Chatterjee, S, Tarrago, M, Clouston, LJ, Sproules, S, Bill, E, Bernales, V, Gagliardi, L, Ye, S, Lancaster, KM & Lu, CC 2019, 'Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes', Inorganic Chemistry, vol. 58, no. 9, pp. 6199-6214. https://doi.org/10.1021/acs.inorgchem.9b00442
Moore JT, Chatterjee S, Tarrago M, Clouston LJ, Sproules S, Bill E et al. Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes. Inorganic Chemistry. 2019 May 6;58(9):6199-6214. https://doi.org/10.1021/acs.inorgchem.9b00442
Moore, James T ; Chatterjee, Sudipta ; Tarrago, Maxime ; Clouston, Laura J. ; Sproules, Stephen ; Bill, Eckhard ; Bernales, Varinia ; Gagliardi, Laura ; Ye, Shengfa ; Lancaster, Kyle M. ; Lu, Connie C. / Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 9. pp. 6199-6214.
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abstract = "Previously, we reported the synthesis of Ti[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ] and the Fe-Ti complex, FeTi[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc + ), respectively. Two isostructural redox members, [FeTiL] + and [FeTiL] - (2 ox and 2 red , respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL] + complex (1 ox ). The solid-state structures of the [FeTiL] +/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 {\AA}, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 {\AA}). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57 Fe M{\"o}ssbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL] +,0,- series are primarily Fe-based and that the polarized Fe-Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13{\%}).",
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AU - Moore, James T

AU - Chatterjee, Sudipta

AU - Tarrago, Maxime

AU - Clouston, Laura J.

AU - Sproules, Stephen

AU - Bill, Eckhard

AU - Bernales, Varinia

AU - Gagliardi, Laura

AU - Ye, Shengfa

AU - Lancaster, Kyle M.

AU - Lu, Connie C

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N2 - Previously, we reported the synthesis of Ti[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ] and the Fe-Ti complex, FeTi[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc + ), respectively. Two isostructural redox members, [FeTiL] + and [FeTiL] - (2 ox and 2 red , respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL] + complex (1 ox ). The solid-state structures of the [FeTiL] +/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57 Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL] +,0,- series are primarily Fe-based and that the polarized Fe-Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).

AB - Previously, we reported the synthesis of Ti[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ] and the Fe-Ti complex, FeTi[N(o-(NCH 2 P( i Pr) 2 )C 6 H 4 ) 3 ], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc + ), respectively. Two isostructural redox members, [FeTiL] + and [FeTiL] - (2 ox and 2 red , respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL] + complex (1 ox ). The solid-state structures of the [FeTiL] +/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57 Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL] +,0,- series are primarily Fe-based and that the polarized Fe-Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).

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