Double-negative ions of rare earth complexes guanidine synthesis
Guanidine ligands has a wealth of coordination chemistry, in the last 20 years of development, people guanidine complexes from the very beginning of the synthesis of various complexes to the most recent of them in the application of catalysis and materials science research, can be described as in the ascendant. It is noteworthy that, despite the expected double-anion complex than a single guanidine anion and neutral complexes with guanidine richer coordination mode and reaction chemistry, but the double anion guanidine complexes are still few reports present , and are concentrated in the transition and main group metals. The reason may be the lack of an effective synthetic method for these complexes. To better understand the double-anion guanidine structure of the complex nature of the characteristics and response, this paper focuses on the negative ions of rare earth double-guanidine complex synthesis, coordination mode and reaction properties. Synthesis and characterization of a total of 46 new rare earth compounds and 39 compounds were determined the crystal structure. Made the following main results:
1. The development of a single through the rare earth complex anion deprotonation of guanidine Preparation of cyclopentadienyl rare earth double-anion complex method of guanidine. First, the use of Cp3Ln neutral guanidine (iPrNH) 2C = NPh reaction synthesis of single ion complex intermediate guanidine Cp2Ln [iPrNC (NPh) NHiPr] [Ln = Yb (2-1), Y (2-2 ), Er (2-3)], and then further deprotonation using BuLi to obtain the corresponding dual-core dual-hybrid ferrocene anion guanidino lanthanide complexes Cp2Ln [(iPrN) 2CNPh] Li (THF) 3 [Ln = Yb (2-10), Y (2-11), Er (2-12)]; Interestingly, under the same conditions, Cp3Ln and (CyNH) 2CNPh reaction, only two isolated guanidine middle of a Mao-rare earth complexes Body CpLn [CyNC (NPh) NHCy] 2 (THF) n [Ln = Yb (2-5), Er (2-6), Gd (2-7)], 2-5 and nBuLi reaction is the formation of a single negative / anion mixed double-guanidine ligands in a Mao-rare earth complexes CpYb [CyNC (NPh) NCy] [(CyN) 2CNPhLi (THF) 3] (2-18), therefore, nitrogen atom substituted with cyclohexyl two lanthanocene double anion Guanidinates Cp2Ln [(CyN) 2CNPh] Li (THF) 3 [Ln = Yb (2-13), Y (2-14), Er (2-15), Dy (2-16) ] need Cp3Ln with equimolar (CyNH) 2CNPh and nBuLi the "pot" reaction; and Cp2Er [(CyN) 3C] Li (THF) 2 (2-17) can also Cp2LnCl and [CyNC (NPh) NHCy] Li and nBuLi were prepared continuous; addition, Cp3Ln and C6H4 [NC (NHCy) 2-1,4] 2, and C6H4 [NC (NHiPr) 2-1,4] 2 reaction, we synthesized benzene biguanide base bridged lanthanide complexes C6H4 [(NC (NCy) NHCy) YCp2 (THF)] 2-1,4 (2-8), and C6H4 [(NC (NiPr) NHiPr) YbCp2] 2-1,4 (2-9), however, tried to de-butyl lithium compounds 2-8 and 2-9 protons on the ligand, the corresponding synthesis of guanidine-bridged double-anion complex has not been successful. Significantly, in exploring the synthesis of cyclopentadienyl rare earth double-anion complexes guanidine new ways, it is also unexpectedly got into the non-silicone product of the expected {[Cp2Y (Me2Si (O) NPh)] [Li (THF) 4 ]} 2 (2-19) and double-carbodiimide insertion products CpYb [nBuC (NCy) 2] [CyN {C (NCy) 2} 2Li (THF)] (2-20).
2. Pioneering study of the cyclopentadienyl rare earth double-anion guanidine complex response properties, found Cp2Ln [(RN) 2CNPh] Li (THF) 3 compounds with chlorosilane reaction of four substituted guanidino lanthanide complexes Cp2Ln [ (RN) 2C (NPhSiMe2R ')] [R = Cy, R' = Me: Ln = Yb (3-1), Ln = Y (3-2), Ln = Er (3-3); R = Cy, R '= tBu: Ln = Yb (3-4), Ln = Er (3-5); R = iPr, R' = tBu: Ln = Yb (3-6), Ln = Er (3-7)] ; further, Cp2Ln [(CyN) 2CNPh] Li (THF) 3 compounds but also with Me2SiCl2 reaction to form first silicon heterocyclic quaternary organic Me2Si (CyN) 2C = NPh (3-8). At the same time, these rare earth coordination with the two anion ligands also won the guanidine protons, into a single guanidine anion ligand. These results show that two-guanidine ligand anion the negative charge is delocalized throughout the CN3 unit structure, with different reaction system, two anion guanidine ligands with active sites on the response variability. It also provides a synthesis of more substituted guanidine method of rare earth complexes.
3. The first of a two-cyclopentadienyl rare earth ion complexes with aromatic guanidine chloride response. Chlorosilane reaction with different, Cp2Ln [(RN) 2CNPh] Li (THF) 3 reacts with ArCOCl amidation / carbodiimide elimination product, indicating that the acylation reaction of guanidine ligand unstable, easily the second carbonation occurs further imine elimination reaction. Significantly, we also found that acylation site is controlled, when R is isopropyl and cyclohexyl, the acylation reaction occurred in the rare earth chelate coordination with the nitrogen atom, the resulting product is [Cp2LnOC (Ar) NR)] 2 [R = iPr, Ar = Ph: Ln = Yb (4-1), Ln = Y (4-2), Ln = Er (4-3), Ln = Dy (4 -4), Ln = Gd (4-5); R = iPr, Ar = 4-ClPh: Ln = Yb (4-6), Ln = Y (4-7), Ln = Er (4-8); R = Cy, Ar = Ph: Ln = Yb (4-9), Ln = Y (4-10), Ln = Er (4-11), Ln = Dy (4-12)]; and when R for the three-dimensional greater steric hindrance of 2,6 - diisopropyl phenyl, acylation reaction occurs with lithium ions on the nitrogen atom, the product is [Cp2YbOC (Ph) NPh)] 2 (4-13). Guanidine ligands into a similar reaction has not been reported in the literature, which not only further illustrates the double-anion reaction of guanidine ligand sites and the potential variability of the rich reaction chemistry, but also for the rare earth complexes and asymmetric amide EDC provides a new method of synthesis.
We supply Magnetic Product,Neodymium magnets,Rare earth magnets,Permanent magnets,in Magnetic Product,Neodymium magnets,Rare earth magnets,Permanent magnets we are your best china magnets suppliers choice.Please contact us!
Xiamen Everbeen Magnet Electron Co.,Ltd. http://www.999magnets.com
Add:Unit H, 4F Rihua Mansion, No. 8 Xinfeng 2nd road, Torch Hi-Tech Zone, Xiamen, China.
Tel:0086-592-5781916
Fax:0086-592-5123653
E-mail:info@china-magnet.net
4. LnCl3 with in situ generated by the two guanidine lithium ion or single negative / mixed double-anion lithium salt guanidine synthesized a series of non-cyclopentadienyl ancillary ligands of the rare earth double-anion Guanidinates {Ln [( iPrN) 2CNPhLi (THF) n] [(iPrN) 2CNPh]} 2 [n = 2: Ln = Yb (5-1), Er (5-2); n = 3: Ln = Er (5-3)] and {Y [(CyN) 3CLi (THF) 2] [(CyN) 3C]} 2 (5-4), and single and double anion anion guanidine guanidine mixed with bits of non-metallocene rare earth complexes {Ln [iPrNC (NPh) iPrNH] [(iPrN) 2CNPh]} 2 [Ln = Yb (5-5), Er (5-6)]. Surprisingly, with the cyclopentadienyl ligand containing dual rare earth ions of different guanidine complexes 5-4, 5-3 and does not react with chlorosilanes.
