Tri(η-cyclopentadienyl)uranium(IV) silyl and siloxide compounds. Crystal structure of [U(η⁵-C₅H₅)₃(OSiPh₃)]. Insertion of lsocyanide into a uranium–silicon bond

Abstract

The complex [U(q5-C5H5), (SiPh,)] (1) has been synthesized from [U(q5-C5H5),CI] and Li(SiPh,) and fully characterized. The direct U-Si bond in (1 ) is quite reactive towards proton acidic molecules, moreover it reacts with 2,6-dimethylphenyl isocyanide to give the insertion product [U(q5-C,H,),{C(NC,H,Me,-2,6)SiPh,}] t Presented by M.

On the Nature of Actinide– and Lanthanide–Metal Bonds in Heterobimetallic Compounds

“…In Table 1, the metal-metal bond distances determined via PBE, CASPT2, and MP2 are compared. Also included in the table are the distances determined via X-ray diffraction [14][15][16][17][18][19][20][21][22][23][24] as well as with the sum of the covalent radii. The covalent radii in Table 1 are taken from the reference by Mantina et al [54] The authors report two sets of covalent radii, those by Cordero et al [55] and those by Pyykkç and Atsumi [56] and they recommend using an average of these values.…”

“…Several systems containing heterobimetallic bonds involving one f-block element were studied computationally. Specifically the following molecules were investigated: [(h 5 -C 5 H 5 ) 2 -A C H T U N G T R E N N U N G (THF)LuRuA C H T U N G T R E N N U N G (h 5 -C 5 H 5 )(CO) 2 ], [19] [(h 5 -C 5 Me 5 ) 2 (I)ThRuA C H T U N G T R E N N U N G (h 5 -C 5 H 5 )(CO) 2 ], [20] [(h 5 -C 5 H 5 ) 2 YReA C H T U N G T R E N N U N G (h 5 -C 5 H 5 ) 2 ], [15] [{N(CH 2 CH 2 NSiMe 3 ) 3 }A C H T U N G T R E N N U N G UReA C H T U N G T R E N N U N G (h 5 -C 5 H 5 ) 2 ], [14] [Y{Ga-A C H T U N G T R E N N U N G (NArCh) 2 }{C(PPh 2 NSiH 3 ) 2 }A C H T U N G T R E N N U N G (CH 3 OCH 3 ) 2 ], [17] [{N(CH 2 CH 2 NSiMe 3 ) 3 }A C H T U N G T R E N N U N G U{GaA C H T U N G T R E N N U N G (NArCH) 2 }A C H T U N G T R E N N U N G (THF)], [18] [(h 5 -C 5 H 5 ) 3A C H T U N G T R E N N U N G UGaA C H T U N G T R E N N U N G (h 5 -C 5 Me 5 )], [16] [YbA C H T U N G T R E N N U N G (h 5 -C 5 H 5 ){SiA C H T U N G T R E N N U N G (SiMe 3 ) 3 -A C H T U N G T R E N N U N G (THF) 2 }], [21] [(h 5 -C 5 H 5 ) 3 UA C H T U N G T R E N N U N G (SnPh 3 )], [22] [(h 5 -C 5 H 5 ) 3 U-A C H T U N G T R E N N U N G (SiPh 3 )], [23] and (Ph[Me]N) 3 USiA C H T U N G T R E N N U N G (SiMe 3 ). [24] Density functional calculations predict geometries in good agreement with experiment.…”

“…While it is not a lanthanide, yttrium is classified as a rare earth element along with scandium and the lanthanides; therefore, YÀM bonds are included in this study. Specifically, calculations were performed for [(h 5 - [19] [(h 5 -C 5 Me 5 ) 2 (I)ThRu-A C H T U N G T R E N N U N G (h 5 -C 5 H 5 )(CO) 2 ], [20] [(h 5 -C 5 H 5 ) 2 YReA C H T U N G T R E N N U N G (h 5 -C 5 H 5 ) 2 ], [15] [14] [17] [{N(CH 2 CH 2 NSiMe 3 ) 3 }- [18] [(h 5 -C 5 H 5 ) 3 UGaA C H T U N G T R E N N U N G (h 5 -C 5 Me 5 )], [16] [21] [(h 5 -C 5 H 5 ) 3 U-A C H T U N G T R E N N U N G (SnPh 3 )], [22] [(h 5 -C 5 H 5 ) 3 UA C H T U N G T R E N N U N G (SiPh 3 )], [23] and (Ph[Me]N) 3 USi-A C H T U N G T R E N N U N G (SiMe 3 ). [24] The ligand choice for each system is described in detail in the respective experimental papers.…”

f-Element silicon and heavy tetrel chemistry

“…The rst report of a complex exhibiting an An-Si bond was in 1989 by Porchia and co-workers, which followed previous reports of germanium and tin analogues (see Section D). [70][71][72] In Fig. 12) by consideration of elemental analysis and mass spectrometry data.…”

Metal–metal bonds in f-element chemistry

“…Interestingly, the reaction of HSnPh 3 with [(h 5 -C 5 H 5 ) 3 U(Me)] or [(h 5 -C 5 H 5 ) 3 U(BH 4 )], or reaction of View Online bond length of 3.166(1) Å , which is well within the sum of the covalent radii for uranium and tin (3.335 Å ). 13 Porchia also reported spectroscopic characterisation of the uranium-silicon 57 and uranium-germanium 58 . Compounds 64 and 65 were both found to react cleanly with HSnPh 3 to afford 63, which was attributed to the greater acid strength of HSnPh 3 compared to the silicon and germanium congeners.…”