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. 2021 Feb 24;27(12):3974-3978.
doi: 10.1002/chem.202003905. Epub 2021 Jan 14.

Synthesis of Unprecedented 4d/4f-Polypnictogens

Niklas Reinfandt  1 , Christoph Schoo  1 , Luis Dütsch  2 , Ralf Köppe  1 , Sergey N Konchenko  1   3 , Manfred Scheer  2 , Peter W Roesky  1
Affiliations

Synthesis of Unprecedented 4d/4f-Polypnictogens

Niklas Reinfandt et al. Chemistry. .

Abstract

A series of 4d/4f-polyarsenides, -polyarsines and -polystibines was obtained by reduction of the Mo-pnictide precursor complexes [{Cpt Mo(CO)2 }2 (μ,η2:2 -E2 )] (E=As, Sb; Cpt =tBu substituted cyclopentadienyl) with two different divalent samarocenes [Cp*2 Sm] and [(CpMe4nPr )2 Sm]. For the reductive conversion of the Mo-stibide only one product was isolated, featuring a planar tetrastibacyclobutadiene moiety as an unprecedented ligand for organometallic compounds. For the corresponding Mo-arsenide a tetraarsacyclobutadiene and a second species with a side-on coordinated As2 2- anion was isolated. The latter can be considered as reaction intermediate for the formation of the tetraarsacyclobutadiene.

Keywords: lanthanides; molybdenum; polyarsenides; polystibides; reduction.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Earlier work: Observed mixture of products in the reduction of [{CpMo(CO)2}2(μ,η 2:2‐P2)]. [5a]
Scheme 2
Scheme 2
Reduction of [{CptMo(CO)2}2(μ,η 2:2‐As2)] with [Cp*2Sm(thf)2] and [(CpMe4nPr)2Sm], resulting in [(Cp*2Sm)2As2(CptMo(CO)2)2] (1) [((CpMe4nPr)2Sm)2As2(CptMo(CO)2)2] (2), and [((CpMe4nPr)2Sm)2As4(CptMo(CO)2)2] (3).
Figure 1
Figure 1
Molecular structure of 1 in the solid state. [22] Hydrogen atoms are omitted for clarity. Selected bond lengths [Å] and angles [°]: Sm1−O1 2.378(4), Sm1−O2′ 2.391(4), Mo1−As1 2.6847(9), Mo1−As1′ 2.6997(9), Mo1−C1 1.892(6), As1−As1′ 2.238(2), C1−O1 1.212(3), O1‐Sm‐O2′ 77.6(2), Mo1‐As1‐Mo1′ 103.92(3).
Figure 2
Figure 2
Molecular structure of 3 in the solid state. [22] Hydrogen atoms are omitted for clarity. Selected bond lengths [Å] and angles [°]: Sm1−As1 3.0300(8), Sm1−O1 2.380(2), Mo1−As2 2.6498(7), Mo1−As1′ 2.6261(7), Mo1−C1 1.873(3), As1−As2 2.4862(7), As1′−As2 2.3503(6), C1−O1 1.206(4), O1‐Sm‐As1 76.99(6), As1′‐Mo1‐As2 52.91(2), Mo1‐As1′‐Sm1′ 142.35(2), As1′‐As2‐Mo1 63.03(2), As1‐As2‐Mo1 105.01(3), As2‐As1‐As2′ 91.16(2), As1‐As2‐As1′ 88.84(2).
Scheme 3
Scheme 3
Synthesis of [(Cp*2Sm)2Sb4(CptMo(CO)2)2] (4) and [((CpMe4nPr)2Sm)2Sb4(CptMo(CO)2)2] (5) with R=Me (4), n‐propyl (5).
Figure 3
Figure 3
Molecular structure of 4 in the solid state. [22] Hydrogen atoms are omitted for clarity. Selected bond lengths [Å], angles [°]: Sm1−Sb2′ 3.2375(7), Sm1−O1 2.381(6), Mo1−Sb2 2.8146(9), Mo1−Sb1 2.8549(9), Mo1−C1 1.894(8), Sb1−Sb2 2.7313(8), Sb1−Sb2′ 2.8608(7), C1−O1 1.209(10), O1‐Sm‐Sb2′ 76.73(14), Sb1‐Mo1‐Sb2 57.59(2), Mo1‐Sb2‐Sm1′ 153.18(2), Sb1‐Sb2‐Mo1 61.94(2), Sb2′‐Sb1‐Mo1 102.32(2), Sb2‐Sb1‐Sb2′ 87.73(2), Sb1‐Sb2‐Sb1′ 92.28(2).
Figure 4
Figure 4
Molecular structure of 5 in the solid state. [22] Hydrogen atoms and solvent molecules (toluene) are omitted for clarity. Selected bond lengths [Å] and angles [°]: Sm1−Sb1 3.2794(8), Sm1−O1 2.386(7), Mo1−Sb2 2.8464(11), Mo1−Sb1′ 2.8315(11), Mo1−C1 1.888(10), Sb1−Sb2 2.8618(10), Sb1′−Sb2 2.7254(10), C1−O1 1.221(12), O1‐Sm‐Sb1 76.8(2), Sb1′‐Mo1‐Sb2 57.37(3), Mo1‐Sb1′‐Sm1′ 152.00(3), Sb1′‐Sb2‐Mo1 61.59(3), Sb1‐Sb2‐Mo1 103.46(3), Sb2‐Sb1‐Sb2′ 90.16(3), Sb1‐Sb2‐Sb1′ 89.84(3).
Figure 5
Figure 5
Energetic relationship of the compounds under discussion. The species „[{CpMo(CO)2}2(μ,η 2:2‐E2)]+[(Cp2*Sm)2P2(CpMo(CO)2)2]+E2“ were taken as reference systems. They were arbitrarily set to identical energies.
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