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• W4225156761 abstract "Here we report a convenient synthesis of new diphosphoramidite ligands derived from 1,8,10,9-triazaboradecalin (TBD) and describe their complexes with group 10 metals. Here we report a convenient synthesis of new diphosphoramidite ligands derived from 1,8,10,9-triazaboradecalin (TBD) and describe their complexes with group 10 metals. Treating the chlorinated and structurally characterized ligand precursor Cl TBDPhos ( L1 ) with four equivalents of HOR (R = C 3 H 7 or C 3 HF 6 ) in the presence of NEt 3 yielded the diphosphoramidite ligands iPrO TBDPhos ( L2 ) and F-iPrO TBDPhos ( L3 ) in good yields. L2 and L3 were used to prepare a variety of Ni, Pd, and Pt complexes with chloride and 1,2-benzenedithiolate ligands so their structures and spectroscopic properties could be compared to similar complexes with methoxy-substituted MeO TBDPhos such as ( MeO TBDPhos)PdCl 2 , which is reported here for the first time. Single-crystal XRD studies on the ( RO TBDPhos)PtCl 2 complexes revealed that increasing the size of alkoxy substituents from MeO to i PrO to F- i PrO decreases the P-M-P bite angle from 97.47(3)° in ( MeO TBDPhos)PtCl 2 to 93.98(4)° in ( F-iPrO TBDPhos)PtCl 2 . Similar changes were observed in the dithiolate complexes ( iPrO TBDPhos)Pt(S 2 C 6 H 4 ) and ( F-iPrO TBDPhos)Pt(S 2 C 6 H 4 ), and the structural studies revealed longer Pt-P bond distances compared to the dichloride complexes that correlated to ca. 1000 Hz decrease in their 195 Pt- 31 P coupling constants. No significant changes were observed in the ligand bond distances in complexes containing the methoxy and isoproxy-substituted ligands, but complexes with fluorinated F-iPrO TBDPhos revealed subtle, but significant differences in their P-N, P-O, and B-N distances that reflect substituent-induced electronic changes in the ligand. Overall, this work establishes a more convenient synthetic entry into the chemistry of alkoxy-substituted TBDPhos ligands for ongoing studies with these and related transition metal complexes." @default.
• W4225156761 created "2022-05-01" @default.
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• W4225156761 date "2022-07-01" @default.
• W4225156761 modified "2023-10-14" @default.
• W4225156761 title "Modular synthesis of diphosphoramidite ligands derived from 1,8,10,9-triazaboradecalin and their complexes with Ni, Pd, and Pt" @default.
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• W4225156761 doi "https://doi.org/10.1016/j.poly.2022.115877" @default.
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