Substitution at boron in molybdaborane frameworks: Synthesis and characterization of isomeric (η5-C5Me5Mo)2B5HnXm (when X=Cl: n=5, 7, 8; m=4, 2, 1 and X=Me: n=6, 7; m=3, 2)

Synthesis of [Mo3S4] Clusters from Half-Sandwich Molybdenum(V) Chlorides and Their Application as Platforms for [Mo3S4Fe] Cubes

“…Analogous phosphine adducts (C 5 Me 4 R)­MoCl 4 (phosphine) (R = Me, Et) have been crystallographically identified . The ESR spectra of 1a – 1c in CH 2 Cl 2 at ambient temperature showed S = 1 / 2 signals at g = 1.992 ( 1a ), 1.982 ( 1b ), and 1.993 ( 1c ) (Table and Figure S7), and these g -values are comparable to those reported for analogues. , The molecular structure of 1b was determined by means of a single-crystal X-ray diffraction study (Figure ). It is interesting and surprising to note that 1b is the first Cp R MoCl 4 complex reported with an X-ray structure, based on our survey through the Cambridge Structural Database.…”

“…The new ligand precursor for 1b , triethyl­(tetramethylcyclopentadienyl)­silane (C 5 Me 4 HSiEt 3 ), was prepared from K­(C 5 Me 4 H) and Et 3 SiCl in toluene and used without further purification. The previously reported synthesis of (C 5 Me 5 )­MoCl 4 includes isolation of the carbonyl-methyl complex (C 5 Me 5 )­Mo­(CO) 3 Me before treatment with PCl 5 . In this study, however, the corresponding complexes with a Cp R ligand were formed as crude dark yellow materials, which were directly subjected to reactions with PCl 5 to reduce the number of manipulations.…”

“…Cp R MoCl 4 (Cp R = C 5 Me 4 SiMe 3 ( 1a ), C 5 Me 4 SiEt 3 ( 1b ), and C 5 Me 4 H ( 1c )) were synthesized in a manner similar to the synthesis of (C 5 Me 5 )­MoCl 4 , on a multigram scale, from sequential reactions of Mo­(CO) 6 with LiCp R in THF under reflux and then with MeI at ambient temperature to furnish a dark yellow solid, followed by treatment with PCl 5 in CH 2 Cl 2 (Scheme ). The new ligand precursor for 1b , triethyl­(tetramethylcyclopentadienyl)­silane (C 5 Me 4 HSiEt 3 ), was prepared from K­(C 5 Me 4 H) and Et 3 SiCl in toluene and used without further purification.…”

Vertex-Fused Metallaborane Clusters: Synthesis, Characterization and Electronic Structure of [(η5-C5Me5Mo)3MoB9H18]

“…The major difference between [{1-(Cp*Ru)(μ-H)B 4 H 9 } 2 Ru] and 2 is that the former has a shorter metal−metal bond distance {2.7930(10) Å} compared to the parent metallaborane [1,2-(Cp*Ru) 2 (μ-H)B 4 H 9 ] {2.8527(4) Å}, while, the latter has longer metal−metal bond distances {3.0481(5)Å, 3.0247(5)Å} compared to its parent metallaborane 1 {2.8085(6) Å}. The intracluster Mo−Mo bond distances of 2.8256(5) and 2.8391(5) Å in 2 are distinctly longer than those reported in [(η 5 -C 5 Me 5 MoCl) 2 B 2 H 6 ] and [(η 5 -C 5 Me 5 Mo) 2 B 5 H 7 (μ 3 -OEt)]; however, they are comparable to those observed in [(η 5 -C 5 Me 5 Mo) 2 B 5 H 9 ] , or [(η 5 -C 5 Me 5 Mo) 2 B 5 H 5 Cl 4 ] …”

Dimetallaheteroborane clusters containing group 16 elements: A combined experimental and theoretical study

“…[(η 5 -C 5 Me 5 )MoCl 4 ] was prepared with some modification 26 of Green's 27 work. Thin layer chromatography was carried on 250 mm dia aluminum supported silica gel TLC plates (MERCK TLC Plates).…”