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Ground-State Singlet L_3Fe-(í-N)-FeL_3 and L_3Fe(NR) Complexes Featuring Pseudotetrahedral Fe(II) Centers

Brown, Steven D. and Peters, Jonas C. (2005) Ground-State Singlet L_3Fe-(í-N)-FeL_3 and L_3Fe(NR) Complexes Featuring Pseudotetrahedral Fe(II) Centers. Journal of the American Chemical Society, 127 (6). pp. 1913-1923. ISSN 0002-7863. doi:10.1021/ja0453073.

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Pseudotetrahedral iron(II) coordination complexes that contain bridged nitride and terminal imide linkages, and exhibit singlet ground-state electronic configurations, are described. Sodium amalgam reduction of the ferromagnetically coupled dimer, {[PhBP_]Fe(μ-1,3-N_3)}_2 (2) ([PhBP_3] = [PhB(CH_2PPh_2)_3]-), yields the diamagnetic bridging nitride species [{[PhBP_3]Fe}_2(μ-N)][Na(THF)_5] (3). The Fe−N−Fe linkage featured in the anion of 3 exhibits an unusually bent angle of approximately 135°, and the short Fe−N bond distances (Fe−N_(av) ≈ 1.70 Å) suggest substantial Fe−N multiple bond character. The diamagnetic imide complex {[PhBP_3]Fe^(II)_≡N(1-Ad)}{^nBu_4N} (4) has been prepared by sodium amalgam reduction of its low-spin iron(III) precursor, [PhBP_3]Fe^(III)_≡N(1-Ad) (5). Complexes 4 and 5 have been structurally characterized, and their respective electronic structures are discussed in the context of a supporting DFT calculation. Diamagnetic 4 provides a bona fide example of a pseudotetrahedral iron(II) center in a low-spin ground-state configuration. Comparative optical data strongly suggest that dinuclear 3 is best described as containing two high-spin iron(II) centers that are strongly antiferromagnetically coupled to give rise to a singlet ground-state at room temperature.

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URLURL TypeDescription ItemSupporting Information
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2005 American Chemical Society. Received August 4, 2004. Publication Date (Web): January 19, 2005. Financial support from the NSF (CHE-0132216), the DOE (PECASE), and the Alfred P. Sloan Foundation is gratefully acknowledged. We thank the Beckman Institute (Caltech) for use of the SQUID magnetometer, and Larry M. Henling and Theodore A. Betley for assistance with crystallographic studies. The Zewail group provided access to a Cary 500 UV/vis/NIR spectrophotometer.
Funding AgencyGrant Number
Department of Energy (DOE)UNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Issue or Number:6
Record Number:CaltechAUTHORS:20140805-132349667
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Official Citation:Ground-State Singlet L3Fe-(μ-N)-FeL3 and L3Fe(NR) Complexes Featuring Pseudotetrahedral Fe(II) Centers Steven D. Brown and and Jonas C. Peters Journal of the American Chemical Society 2005 127 (6), 1913-1923
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:47995
Deposited By: Ruth Sustaita
Deposited On:05 Aug 2014 20:43
Last Modified:10 Nov 2021 17:52

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