High nitrogen gas generant compositions, useful for inflating passenger restraint gas inflator bags, comprise a nitrogen rich coordination compound selected from coordination complexes comprised of anionic nitro and nitrito ligands coordinated with a transitional metal template, and nonmetallic or nonmetallic/metallic cations. The gas generant compositions generate relatively more gas and less solids, and are safer than known gas generant compositions. Certain gas generant compositions ignite at lower autoignition temperatures thereby facilitating the use of an aluminum or light weight metal pressure vessel. Other gas generants self-deflagrate eliminating the need for other constituents in the composition. Novel methods for the synthesis of nonmetal derivative coordination complexes, guanidine and hydrazine for example, are also presented.