The reaction of adamantane with PCl3/A1Cl3, followed by hydrolysis, gave (1-Ad)2P(:O)Cl 1, which was converted to (1-Ad)2P(:O)F 2 and (1-Ad)2P(:S)Cl 3 by standard procedures. The structure of 1 was confirmed by a single crystal X-ray structure determination; despite the bulky substituents the P-C bond lengths are normal (184.0(3), 185.0(3) pm). Whereas chlorine-fluorine exchange in 3 with AsF3 furnished (1-Ad)2P(:S)F 4, desulfuration of 3 with Ph3P to give (1-Ad)2PCl 5 failed. The secondary phosphine oxides R 1R2P(:O)H (R1, R2 = 1-Ad: 6; R1 = 1-Ad, R2 = tBu: 7; R1, R2 = tBu: 8) were synthesized by reaction of 1, 1-AdP(:O)Cl2 and tBuP(:0)Cl2 with tBuLi. 6 and 8 reacted readily with chloral to give the adducts R2P(:O)CH(OH)CCl3 (R = 1-Ad: 9; R = tBu: 10). Silylation of 6 with Me2NSiMe3 in the presence of dry air led to (1-Ad)2P(:O)OSiMe3 11, which was hydrolyzed to give (1-Ad)2P(:O)OH 12. (1-Ad)2POSiMe3 13 was obtained by the reaction of 6 with n-BuLi, followed by Me3SiCl. No reaction took place upon heating 6 with Mo(CO)6. (1-Ad)2PCl 5 was synthesized in low yield by the reaction of 6 with PCl3. The action of tetrachloro-obenzoquinone (TOB) upon 6 furnished (1-Ad)2P(:O)(o-OH)C6Cl4 15, whereas the tbutyl analogue of 15, 16, was synthesized by hydrolysis of the TOB-adduct of di-tbutylfluorophosphine. Analogous 1-adamantyl- and tbutyl-phosphorus compounds are compared with regard to their 31P NMR data
Tertiary alkyl halides as growth activator and inhibitor for novel atomic layer deposition of low resistive titanium nitride