Coordination complexes that pair a zero-valent transition metal (Ni, Co, Fe) and an aluminum(III) center have been prepared. They add to the few examples of structurally characterized metal alanes and are the first reported metallalumatranes. To understand the M-Al interaction and gauge the effect of varying the late metal, the complexes were characterized by X-ray crystallography, electrochemistry, UV-Vis-NIR and NMR spectroscopies, and theoretical calculations. The M-Al bond strength decreases with varying M in the order Ni > Co > Fe.

In the field of metal-metal bonding, the occurrence of stable, multiple bonds between different transition metals is uncommon, and is largely unknown for different first-row metals. Adding to a recently reported iron-chromium complex, three additional M-Cr complexes have been isolated, where the iron site is systematically replaced with other first-row transition metals (Mn, Co, or Ni), while the chromium site is kept invariant. These complexes have been characterized by X-ray crystallography. The Mn-Cr complex has an ultrashort metal-metal bond distance of 1.82 Å, which is consistent with a quintuple bond. The M-Cr bond distances increases across the period from M = Mn to M = Ni, as the formal bond order decreases from 5 to 1. Theoretical calculations reveal that the M-Cr bonds become increasingly polarized across the period. We propose that these trends arise from increasing differences in the energies and/or contraction of the metals' d-orbitals (M vs Cr). The cyclic voltammograms of these heterobimetallic complexes show multiple one-electron transfer processes, from two to four redox events depending on the M-Cr pair.

Figure 3. Qualitative MO diagram of the d-orbital manifold for 1 and 2, shown with the dominant electronic configurations (CASSCF).

Anionic cobalt and iron metallalumatranes that bind dinitrogen in an end‐on fashion were prepared and characterized by X‐ray crystallography. Along with literature‐known neutral cobalt and iron metallalumatranes, they form a quartet of low‐valent coordination complexes for comparing dinitrogen activation and functionalization at cobalt versus iron centers. In the anionic metallalumatranes, the metal atoms are proposed to have subvalent oxidation states of –1. The electronic structure of the anionic iron alumatrane, which was probed by electron paramagnetic resonance spectroscopy, Mössbauer spectroscopy, and density functional theory, is most consistent with Fe(–1)→Al(+3). Functionalization of dinitrogen was achieved by reaction of the ferrate alumatrane with 1,2‐bis(chlorodimethylsilyl)ethane and KC8 (1 equiv.) to generate an iron(II) disilylhydrazido complex. The transformation of dinitrogen to disilylhydrazido(2–) is an overall four‐electron process.

Into the metalloligand Cr[N(o-(NCH2P(iPr)2)-C6H4)3] (1, CrL) was inserted a second chromium atom to generate the dichromium complex Cr2L (2), which is a homobimetallic analogue of the known MCrL complexes, where M is manganese (3) or iron (4). The cationic and anionic counterparts, [MCrL]+ and [MCrL]−, respectively, were targeted, and each MCr pair was isolated in at least one other redox state. The solid-state structures of the [MCrL]+,0,− redox members are essentially the same, with ultrashort metal–metal bonds between 1.96 and 1.74 Å. The formal shortness ratios (r) of these interactions are between 0.84 and 0.74 and are interpreted as triple to quintuple metal–metal bonds with the aid of theory. The trio of (d–d)10 species [Cr2L]− (2red), MnCrL (3), and [FeCrL]+ (4ox) are S = 0 diamagnets. On the basis of M—Cr bond distances and theoretical calculations, the strength of the metal–metal bond across the (d–d)10 series increases in the order Fe < Mn < Cr. The methylene protons in the ligand are shifted downfield in the 1H NMR spectra, and the diamagnetic anisotropy of the metal–metal bond was calculated as −3500 × 10−36, −3900 × 10−36, and −5800 × 10−36 m3 molecule−1 for 2red, 3, and 4ox respectively. The magnitude of diamagnetic anisotropy is, thus, affected more by bond polarity than by bond order. A comparative vis–NIR study of quintuply bonded 2red and 3 revealed a large red shift in the δ4 → δ3δ* transition energy upon swapping from the (Cr2)2+ to the (MnCr)3+ core. Complex 2red was further investigated by resonance Raman spectroscopy, and a band at 434 cm−1 was assigned as the Cr—Cr bond vibration. Finally, 4ox exhibited a Mössbauer doublet with an isomer shift of 0.18 mm/s that suggests a primarily Fe-based oxidation to Fe(I).

In engem Kontakt: Die ersten Beispiele von M‐M‐Mehrfachbindungen zwischen unterschiedlichen Übergangsmetallen der ersten Reihe werden vorgestellt (siehe Bild; Fe magenta, Cr grün, P gelb, N blau). Die Bindung wurde durch Röntgenkristallographie, spektroskopische Methoden und Rechnungen analysiert. Die Komplexe zeigen sehr kurze Fe‐Cr‐Bindungen (<2 Å; hoch delokalisierte σ‐ und π‐Beiträge) sowie ungewöhnlich große Quadrupol‐Aufspaltungen.