Two series of boron derivatives with propiolamidinato ligands, [BPh2{C(C≡CAr)(NR)2}] (Ar = Ph, p-MeOPh, p-FPh, p-Me2NPh, or phen; R = iPr or p-tolyl), were synthesized and structurally characterized. The corresponding propiolamidine (or propargylamidine) proligands have been obtained through sustainable methods. One is the catalytic hydroalkynylation of diisopropylcarbodiimide with different terminal alkynes, using simple ZnEt2 as a precatalyst. Alternatively, to obtain propiolamidines with aromatic groups on the nitrogen atoms, the formation of lithiated derivatives of terminal alkynes by reaction with n-BuLi in air and at room temperature, and subsequent addition to the di-p-tolylcarbodiimide, under the same conditions and using 2-MeTHF as a sustainable solvent, has been used for the first time. After reaction with BPh3, the corresponding boron amidinates were obtained, which are emissive in the solution state. The influence of the different substituents introduced into the ligands on the photophysical properties of the boron compounds has been studied. One of the obtained compounds can be used as a ratiometric fluorescent pH sensor in the acidic range.